Section outline

  • General

  • UNIT 1 INTRODUCTION TO ORGANIC CHEMISTRY

    Key unit competency

    Apply IUPAC rules to name organic compounds and explain types of isomers for

    organic compounds

    Learning objectives

    Classify organic compounds as aliphatic, alicyclic and aromatic

    Determine different formulae for given organic compounds

    Describe the common functional groups and relate them to the homologous series

    Use IUPAC rules to name different organic compounds

    Describe the isomers of organic compounds


    Introductory activity

    Consider the following substances: Sodium chloride, starch, table sugar,

    magnesium carbonate, glucose, sodium hydrogen carbonate, water.

    1. Heat a small sample of each ( 5g for solids, 5ml for liquids) in a crucible

    2. Record your observations.

    3. From the observations, classify the substances listed above.

    4. What criterion do you use for that classification?

    5. Interpret your observations

    Organic chemistry is defined as the study of the compounds mainly composed by

    carbon and hydrogen atoms, and sometimes oxygen, nitrogen, phosphorus, sulphur

    and halogens atoms. The study of the rest of the elements and their compounds falls

    under the group of inorganic chemistry. However, there are some exceptions such

    as carbonates, cyanides, carbides, carbon oxides, carbonic acid, carbon disulphide

    which are considered as inorganic compounds. Since various organic compounds

    contained carbon associated with hydrogen, they are considered as derived from

    hydrocarbons. Thus, a more precise definition of organic chemistry is: “the study of

    hydrocarbons and the compounds which could be thought of as their derivatives’’.

    The organic and inorganic compounds can be differentiated based on some of their

    properties as summarised in the following table.



    Why to study organic chemistry as a separate branch?

    The organic chemistry involves the study of all chemical reactions that are commonly

    used in industries and many other organic reactions that take place in living systems.

    Materials used in everyday life, food processing and other manufacturing objects are

    obtained based on organic chemistry. Some other reasons are highlighted below.

    Large number of compounds: up to now, no one knows exactly the number

    of organic compounds that are present in nature.

    Built of relatively few elements: The elements frequently encountered

    in organic compounds are carbon, hydrogen, oxygen, nitrogen, sulphur,

    phosphorous, and halogens;

    Unique characteristic of carbon to undergo catenation: carbon atom is

    unique among other elements whose atoms possess the capacity to unite

    with each other by the covalent bonds resulting in a long chain of carbons ( i.e:

    polysaccharides, proteins, polyesters, polyamides…).

    Isomerism is the existence of compounds that have the same molecular formula

    but different arrangements of atoms; these compounds are called “isomers”.

    Functional groups as basis of classification: Organic molecules contain

    active atoms or groups of atoms which determine their chemical behaviour.

    These are called functional groups joined in a specific manner. Therefore,

    organic compounds with similar functional groups display similar properties and form a class


    Combustibility: organic compounds are combustible.

    Nature of chemical reactions: organic compounds being formed by covalent

    bonds, they are slow and often have a low yield.

    Importance of organic chemistry

    The organic chemistry is a subject that plays an important role in modern life. In

    general, there is no art, science or industry where knowledge of organic chemistry

    is not applied.

    Examples where organic chemistry is applied:

    1)Application in daily life.

    In our day-to-day life, we find many substances or materials that are commonly used

    and the later are made of organic compounds.

    Food: starch, fats, proteins, vegetables,...

    Clothes: cotton, wool, nylon, dacron, ....

    Fuels: petrol, diesel oil, and kerosene

    Dyes of all kinds

    Cosmetics (body lotion,…)

    Soaps and detergents

    Medicine: cortisone, sulphonamide, penicillin,…

    Drugs: morphine, cocaine,...

    Stationery: pencils, paper, writing ink,…

    Insecticides,rodenticides,ovicides …

    2)Applications in industry

    The knowledge of organic chemistry is required in many industries such as

    manufacture of food, pharmacy, manufacture of dyes and explosives, alcohol

    industry, soil fertilisers, petroleum industry, etc.


    3)Study of life processes

    Organic chemistry in other words is the chemistry of life. For example the vitamins, enzymes, proteins and hormones are important organic compounds

    produced in our body to ensure its proper development.






    (https://chemistry.tutorvista.com/organic-chemistry/hydrocarbons.html)


    1.1.1. Aliphatic compounds

    Aliphatic compounds are organic compounds in which the carbon atoms are

    arranged in a straight or branched chain.



    1.1.2. Alicyclic compounds

    Alicyclic compounds are organic compounds that contain one or more carbon rings

    that may be saturated or unsaturated



    1.1.3. Aromatic compounds

    Aromatic compounds are compounds that contain a closed ring that consists of

    alternating single and double bonds with delocalised pi electrons.



    Aromatic compounds are designated as monocyclic, bicyclic and tricyclic if they

    contain one, two or three rings, respectively.

    Examples:



    Note: Heterocyclic compounds: Are also classified as cyclic compounds which

    include one or two atoms other than carbon (O, N, S) in the ring.Thus furan, thiophene

    and pyridine are heterocyclic compounds.





    1.2. Types of formulas for organic compounds



    Atoms bond together to form molecules and each molecule has a chemical formula.

    In organic chemistry, we can distinguish empirical, molecular and structural formulas.

    1.2.1. Empirical formula

    The empirical formula is the simplest formula which expresses the ratio of the number

    of atoms of each element present in a particular compound. The empirical formula

    is determined using the percentage composition according to the following steps.

     i. The percentage of each element, considered as grams of that element in 100g

    of the compound, is divided by its atomic mass. This gives the number of moles

    of the element in 100g of the compound.

     ii. The result in i. is then divided by the lowest ratio (number of moles in 100g of

    the compound), seeking the smallest whole number ratio.

     iii. If the atomic ratios obtained in ii. are not the whole number, they should be

    multiplied by a suitable common factor to convert each of them to the whole

    numbers (or approximatively equal to the whole numbers). Minor fractions are

    ignored by rounding up or down (ex: 7.95 = 8).




    1.1.2. Molecular formula

    The molecular formula is a formula expressing the exact number of atoms of each

    element present in a molecule.

    Molecular formula = Empirical formula x n 



    Example 1:

    An organic compound contains 31.9% by mass of carbon, 6.8% hydrogen and 18.51%

    nitrogen and the remaining percentage accounts for oxygen. The compound has a

    vapour density of 37.5. Calculate the molecular formula of that compound.




    Vapour density = a half molecular mass

    Molecular mass = 2 x vapour density = 2 x 37.5 = 75g/mol




    Note: From the above calculations, we can extend our generalized expression: : From the above calculations, we can extend our generalized expression:

    % of Oxygen = 100 – (% hydrohen + % carbon)

    1.2.3. Structural formulas

    Structural formula shows how the different atoms in a molecule are bonded (i.e.

    linked or connected)

     There are three types of structural formulas: displayed, condensed and skeletal

    (stick) formulas.




    1.3. Functional groups and homologous series

    1.3.1 Functional groups



    A functional group is an atom or group of atoms in a molecule which determines

    the characteristic properties of that molecule. Examples of some fuctionnal groups

    are indicated in the Table 1.2.


    1.3.2. Homologous series



    When members of a class of compounds having similar structures are arranged in

    order of increasing molecular mass, they are said to constitute a homologous series.

    Each member of such a series is referred to as a “homologous” of its immediate

    neighbours. For example, the following sequence of straight chain of alcohols forms

    a homologous series.




    Characteristics of a homologous series

    1. Any member of the series differs from the next by the unit –CH2-(methylene group)

    2. The series may be represented by a general formula of alcohols which is

    CnH2n+1 OH where n =1,2,3, etc.

    3. The chemical properties of the members of a homologous series are

    similar, though in some series the first members show different behaviour.

    4. The physical properties such as density, melting point and boiling point

    generally increase within the molecular mass.




    1.4. General rules of nomenclature of organic compounds according to IUPAC



    The organic compounds are named by applying the rules set by the International

    Union of Pure and Applied Chemistry (IUPAC). The purpose of the IUPAC system of

    nomenclature is to establish an international standard of naming compounds to

    facilitate the common understanding.

    In general, an IUPAC name has three essential parts:

    A prefix that indicates the type and the position of the substituents on the

    main chain.

    The base or root that indicates a major chain or ring of carbon atoms found

    in the molecule’s structure. e.g. Meth- for one carbon atom, eth- for 2 carbon

    atoms, prop- for 3 carbon atoms, hex- for five carbon atoms, etc.

    The suffix designates the functional group.

    Example -ane for alkanes, -ene for alkenes, -ol for alcohols, -oic acid for carboxylic

    acids and so on.

    Steps followed for naming organic compounds:

    1. Identify the parent hydrocarbon:

    It should have the maximum length, or the longest chain




    3. Identification of the side chains.

    Side chains are usually alkyl groups. An alkyl group is a group obtained by a

    removal of one hydrogen atom from an alkane. The name of alkyl group is obtained

    by replacing -ane of the corresponding alkane by yl (Table 1.3).




    4.If the same substituent occurs two or more times, the prefix di, tri,tetra, ...is

    attached to substituent’s name. Its locants separate the prefix from the name of the

    substituent.


    5.Identify the remaining functional groups, if any, and name them. Different side

    chains and functional groups will be listed in alphabetical order.


    The prefixes di, tri, tetra,...are not taken into consideration when grouping

    alphabetically. But prefixes such iso-, neo- are taken into account.

    Example:


    Identify the position of the double/triple bond.

    Example:


    The sum of the numbers which show the location of the substituents is the possible smallest




    The correct name will be the one which shows the substituents attached to the third

    and fifth carbon, respectively and not to the fourth and the fiveth carbon atom.

    Numbers are separated by commas Hyphens are added between numbers and

    words. Successive words are merged in one word.






    1.5. Isomerism in organic compounds




    Isomerism is the existence of compounds that have the same molecular formula

    but different arrangements of atoms; these compounds are called “isomers”.

    Isomers have different physical or/and chemical properties and the difference may

    be great or small depending on the type of isomerism.

    There are two main classes of isomerism: Structural isomerism and stereoisomerism.


    1.5.1. Structural isomerism



    1. Position isomerism

    Position isomers are compounds with the same molecular formula but different

    positions of the functional group or substituent(s).

    2. Chain isomerism

    Chain isomers are compounds with the same molecular formula, belonging to the

    same homologous series, with chain of carbon atoms of different length.


    3. Functional isomerism

    Functional (group) isomers are compounds which have the same molecular formula

    but different functional groups.

    Examples:


    1.5.2. Stereoisomerism


    1. Geometrical isomerism

    Geometrical isomers or cis-trans isomers are compounds with the same molecular

    formula, same arrangement of atoms but differ by spatial arrangements.

    This type of isomers is mainly found in alkenes due to the restricted rotation around

    the carbon-carbon double bond.

    Note: For more information, visit the website below. (https://www.youtube.com/

    watch?v=7tH8Xe5u8A0).

    The necessary condition for an alkene to exhibit geometrical isomerism is that each

    carbon doubly bonded has two different groups attached to it.



    2. Optical isomerism


    Optical isomers are compounds with the same molecular formula and arrangements

    of atoms but have different effect on the plane polarised light.

    A compound that rotates the plane polarised light is said to have an optical activity.

    This type of isomerism occurs in compounds containing an asymmetric

    (asymmetrical) carbon atom or chiral centre1.

    .

    When a molecule has chiral centre, there are two non superimposable isomers

    that are mirror images of each other.

    Such compounds are called enantiomers




    In a mirror, the left hand is the image of the right hand and they are non

    superimposable, i.e. they are enantiomers. An achiral object is the same as its mirror

    image, they are nonsuperimposable.











    Activities: 5
  • Unit 2 : ALKANES

    UNIT 2: ALKANES

    Key unit competency

    Relate the physical and chemical properties of the alkanes to the preparation

    methods, uses and isomerism.

    Learning objectives

    Name straight chain alkanes up to carbon-20

    Define homologous series

    Use IUPAC system to name straight and branched alkanes

    Describe the preparation methods of the alkanes

    Prepare and collect methane gas

    Respect of procedure in experiment to carry out preparation of methane or propane

    Describe and explain the trend in physical properties of homologous series ofalkanes

    Be aware of the dangers associated with combustion reactions of the alkanes

    Write reaction for free radical mechanism for a photochemical reaction

    State the chemical properties of the alkanes

    Develop practical skills,interpret results make appropriate deductions.

    Appreciate the importance of the alkanes in daily life

    Appreciate the dangers caused by the alkanes to the environment as major

    sources of air contaminants

    State the uses of the alkanes




    Alkanes are the simplest class of organic compounds. They are made of carbon and

    hydrogen atoms only and contain two types of bonds, carbon-hydrogen (C-H) and

    carbon-carbon (C-C) single covalent bonds. They do not have functional groups.

    Alkanes form a homologous series with the general formula CnH2n+2 where n is the

    number of carbon atoms in the molecule. The first member of the family has the

    molecular formula CH4 (n=1) and is commonly known as methane and the second

    member with molecular formula is C2H6 (n=2) is called ethane.


    These compounds are also known as saturated hydrocarbons. This name is more

    descriptive than the term “alkane’’ because both their composition (carbon and

    hydrogen) and the fact that the four single covalent bonds of each carbon in their

    molecules are fully satisfied or ‘’saturated’’.


    The name alkane is the generic name for this class of compounds in the IUPAC

    system of nomenclature. These hydrocarbons are relatively unreactive under

    ordinary laboratory conditions, but they can be forced to undergo reactions by

    drastic treatment. It is for this reason that they were named paraffins (Latin parum

    affinis = little activity).


    2.1. Nomenclature of alkanes




    IUPAC Rules for the nomenclature of alkanes

    a. Find and name the longest continuous carbon chain.

    b. Identify and name groups attached to this chain.

    c. Number the chain consecutively, starting at the end nearest a substituent

    group.

    d. Designate the location of each substituent group by an appropriate

    number and name.

    e. Assemble the name, listing groups in alphabetical order. The saturated

    hydrocarbon form homologous series (series in which members have similar

    chemical properties and each differs from the preceding by a methylene

    group –CH2-).

    The first four members are known by their common names, from C5 and

    above the Roman prefixes indicating the number of carbon atoms is written

    followed by the ending “ane” of the alkanes.

    Note: Alkyl groups are obtained when one hydrogen atom is removed from

    alkanes; therefore their names are deduced from the corresponding alkanes

    by replacing “ane” ending with “yl” desinence (Table 2.1)




    Prefixes di, tri, tetra, sec, tert, are not considered when alphabetizing.

    f. In case of chains of the same length, the priority is given for part where

    many branched of alkyl groups appear.


    g. For cyclanes or cycloalkanes, the prefix “cyclo” is recommended, followed
    by the name of the alkanes of the same carbon number.

       But in case of ramified cyclanes, the priority is for the ring.





    Note: If there are more than one substituent, the numbering is done so that the

    sum of the numbers used to locate the locants is minimum. This is the lowest sum

    rule.






    2.2. Isomerism



    Alkanes show structural isomerism. The easiest way to find isomers is to draw the

    longest chain of carbon atoms first and then reduce it by one carbon first until

    repetition begins to occur.



    d. Substitute one hydrogen on carbon (3) by the mathyl group


    e.Longest chain reduced further to 4 carbon atoms by cutting 2 methyl group



    -Putting the methyl group on position 1 or 5 gives you the same straight chain

    isomer.


    2.3 Occurrence of Alkanes



    1. The alkanes exist in nature in form of natural gases and petroleum. Natural

    gas and petroleum existence are the results of decomposition of died

    bodies after many years ago.

    2. The most natural gas is found in lake Kivu as methane gas but in form of

    traces like ethane, propane and butane

    3. Petroleum is the most world energy, it is formed by decomposition by

    bacteria for millions of years died marine living things and as the last

    product is petroleum and natural gases which are separated in fractional

    distillation of their crude oil and the results are obtained according to their

    boiling point. 






    2.4. Preparation of alkanes






    Note: The reaction is practically used to reduce by one carbon the length of carbon chain. It is referred as decarboxylation of sodium carboxylates.

    Other reactions used for the preparation of alkanes are the following:

    1. Addition reaction of hydrogen to alkenes and alkynes in the presence of

    catalyst like Nickel, Palladium or platinum produces alkanes: this reaction

    is called hydrogenation reaction of alkenes and alkynes; it is also called a

    reduction reaction of alkenes and alkynes.



    2. From halogenoalkanes or Alkyl halides

     On reduction of alkyl halides with Zn and concentrated hydrochloric acid, alkyl

    halides are converted to alkanes. 




    b) Alkyl halides when heated with sodium metal in ether solution give higher alkanes (alkanes with more carbon atoms) (Wurtz reaction).


    c) When Alkyl halides are treated with Zn-Cu couple, in the presence of ethanol,

    alkanes are formed.

    Note: Zn-Cu couple is obtained by adding Zinc granules in aqueous copper (II)

    sulphate solution where copper is deposited on the Zn pieces. 



    3. From carbonyl compounds

    Reduction of carbonyl compounds, with amalgamated Zinc (alloy made of zinc

    and mercury) and HCl. This is the Clemmensen reduction). 





    2.5. Physical properties of alkanes





    The above Table shows that the boiling and melting points of homologue alkanes

    increase with the number of carbon i.e. molecular mass.

    Explanation:

    The boiling and melting points depend on the magnitude of the Van Der Waal’s

    forces that exist between the molecules. These forces increase in magnitude with

    molecular mass. 


    Note: Branched chain isomers have lower boiling and melting points than their

    straight chain isomers, because straight chain isomers are closer packed than the

    branched chain isomers.




    2.6. Chemical properties of alkanes



    Generally, alkanes are quite inert towards common reagents because:

    The C-C bond and C-H bonds are strong and do not break easily.

    Carbon and hydrogen have nearly the same electronegativity valuehence

    C-H bond only slightly polarized; generally C-H bond is considered as covalent.

    They have unshared electrons to offer.

    They, however, undergo the following reactions.

    1. Reaction with oxygen

    Alkanes react with oxygen to produce carbon dioxide (if oxygen is enough to

    burn all quantity of hydrocarbons), or carbon monoxide or carbon if oxygen is in

    insufficient quantity, and water. This reaction is called “combustion”



    Carbon dioxide (CO2) produced from the burning of alkanes or fossil fuels for heating, transport and electricity generation is the major atmospheric pollutant that increases the green house potential of the atmosphere .Carbon dioxide is the major Green House Effect (GHE) gas.

    Burning wood and forests produce also carbon dioxide and lead to the increase of that gas in the atmosphere. Methane as another GHE gas is produced by human activities, agriculture (Rice), and cattle-rearing.


    There are many natural ways of reducing atmosphere carbon dioxide:

    i. Water in seas dissolves millions of tonnes of gas (but less now than it did in

    the past, since the average ocean temperature has increased by 0.5 oC in the last 100 years, and gases are less soluble in hot than in cold water).

    ii. Plankton can fix the dissolved carbon dioxide into their body mass by photosynthesis

    iii. Trees fix more atmospheric carbon dioxide than do grass and other vegetation through photosynthesis according to the equation below.


    There are other ways than natural ways of reducing GHE gases and among them

    there are the use of technologies that reduce the green house gas emissions, the

    recycling of the GHE.

    Notice: (i) Br2

     reacts as Cl2

     but slowly while iodine reacts hardly or does not.

    Notice: (i) Br2 reacts as Cl2 but slowly while iodine reacts hardly or does not

    ,Fluorine, the most electronegative element of the periodic table reacts with

    alkanes to give coke,

    i.e. a decomposition reaction:



    A mechanism of a reaction is a description of the course of the reaction which

    shows steps of the reaction and the chemical species involved in each step.


    The mechanism for the reaction between methane and bromine is the following:




    (ii) Due to radical formation involved, the main product of reaction is the one from

    the most stable radical, starting with tertiary, secondary, primary and methyl in

    decreasing order of stability.


    A tertiary free radical is better stabilised by the electron donating methyl groups

    than the secondary, primary and methyl ones where the carbon atom is attached

    to more hydrogen atoms


    3. Dehydrogenation of alkanes gives alkenes under heat and a catalyst like V2O5


    4. Cracking

    On heating or in the presence of a catalyst, large molecules of alkanes are

    decomposed into smaller alkanes and alkenes. If the cracking is performed on

    heating, it is referred as themocracking.


    If the cracking is performed using a catalyst; it is referred as catalytic cracking and

    many products result from one reactant as shown below.




    2.7. Uses of alkanes



    1. Methane (CH4)

    Methane finds many uses:

    It is used as a fuel at homes, ovens, water heaters, kilns and automobiles as it

    combusts with oxygen to produce heat.

    Highly refined liquid methane is used as rocket fuel.

    Methane is used as fuel for electricity generation.

    It is used as a vehicle fuel in the form of liquefied natural gas (LNG).

    Methane can be used as raw material in the production of urea, a fertilizer.

    In general, methane is more environmental friendly than gasoline/petrol and

    diesel.

    2. Butane (C4H10)

    Butane is a key ingredient of synthetic rubber.

    It is used as fuel in cigarette lighters.

    When blended with propane and other hydrocarbons, it may be referred to

    commercially as LPG, for liquefied petroleum gas.

    Butane gas cylinders are used in cooking.

    Also used in aerosol spray cans.

    3. Propane (C3H8)

    Propane is used as a propellant for aerosol sprays such as shaving creams

    and air fresheners.Used as fuel for home heat and back up electrical

    generation in sparsely populated areas that do not have natural gas

    pipelines.

    Propane is commonly used in movies for explosions

    4. Ethane (C2H6)

    Ethane is used in the preparation of ethene and certain heavier

    hydrocarbons.

    Ethane can be used as a refrigerant in cryogenic refrigeration systems.

    5. Pentane (C5H12)

    Pentane is used in the production of polystyrene foams and other foams.

    Used in laboratories as solvents.

    It is also an active ingredients of pesticides.

    Used as solvent in liquid chromatography

    6. Hexane (C6H14)

    It is used in the formulation of glues for shoes, leather products, and roofing.

    It is also used to extract cooking oils such as canola oil or soy oil from seeds.

    Hexane is used in extraction of pyrethrine from pyrethrum; e.g. Horizon

    SOPYRWA (a pyrethrum factory in Musanze District).

    Also for cleansing and degreasing a variety of items, and in textile

    manufacturing.

    7. Heptane (C7H16)

    Heptane is used as solvent in paints and coatings.

    Pure n-heptane is used for research, development and pharmaceutical

    manufacturing

    Also as a minor component of gasoline.

    It is used in laboratories as a non-polar solvent.



    Activities: 0
  • UNIT 3: ALKENES AND ALKYNES

    Key unit competency

    Relate the physical and chemical properties of alkenes and alkynes to their

    reactivity and uses

    Learning objectives

    Explain the reactivity of alkenes in comparison to alkanes

    Explain the existence of geometrical isomerism in alkenes

    Describe the industrial process of preparing alkenes and alkynes

    Apply IUPAC rules to name alkenes and alkynes

    Carry out an experiment to prepare and test ethene gas

    Outline the mechanisms for electrophilic addition reactions for alkenes and

    alkynes

    Write the structural formulae of straight chain alkenes and alkynes

    Apply Markovnikov’s rule to predict the product of hydrohalogenation of

    alkenes

    Classify alkynes as terminal and non-terminal alkynes using their different

    structures

    Appreciate the combustion reaction as source of fuels.

    Appreciate the uses and dangers of addition polymers (polythene used for

    polythene bags, polypropene for plastic bottles etc.)


    Introductory activity

    Observe the following picture and answer the questions that follow.



    1. What is the collective name of the substances used to manufacture the

    items showed in the above picture?

    2. a. What are the raw materials used in the manufacture of the substances

    identified in 1)?

    b. These raw materials may be obtained from different sources. Discuss

    this statement.

    c. Do you expect these raw materials be soluble or not in water? Justify

    your answer.

    3. Even though the items which appear in the picture above are interesting,

    they also present some disadvantages. Discuss this statement.


    3.1. Definition, structure and nomenclature of alkenes


    Alkenes are a homologous series of hydrocarbons which contain a carbon-carbon

    double bond. Since their skeleton can add more hydrogen atoms, they are referred

    as unsaturated hydrocarbons.

    The general formula of alkenes is CnH2n.


    Alkenes are abundant in the nature and play important roles in biology. Ethene,

    for example, is a plant hormone, a compound that controls the plant’s growth and

    other changes in its tissues.

    Ethene affects seed germination, flower maturation, and fruit ripening.

    They are described as unsaturated hydrocarbons because they can undergo

    addition reactions.

    The double bond in alkenes is made of one sigma bond and one pi bond. This gives rise to the impossibility of rotation around the double bond. The hybridization state in alkenes is sp2 and the structure around each carbon doubly bonded is trigonal planar with a bond angle value of 120o


    .IUPAC names of alkenes are based on the longest continuous chain of carbon

    atoms that contains the double bond.

    The name given to the chain is obtained from the name of the corresponding

    alkane by changing the suffix from –ane to ene.

    If the double bond is equidistant from each end, number the first substituent that

    has the lowest number. If there is more than one double bond in an alkene, all of

    the bonds should be numbered in the name of the molecule, even terminal double

    bonds. The numbers should go from lowest to highest, and be separated from one

    another by a comma.

    The chain is always numbered from the end that gives the smallest number for the

    location of the double bond.

    In naming cycloalkenes, the carbon atoms of the double bond are numbered

    1 and 2 in the direction that gives the smallest numbers for the location of the

    substituents.

    If a compound contains two or more double bonds, its location is identified by a

    prefix number. The ending is modified to show the number of double bonds:

    a diene for two double bonds,

    a triene for two three bonds

    a tetraene for four double bonds





    3.2. Isomerism in alkenes


    Alkenes exhibit two types of isomerism: structural isomerisms and

    stereoisomerism.

    1. Structural isomerism

    Alkenes show as well position isomerism, chain isomerism and functional isomerism.

    In position isomerism, the position of the double bond changes but the length

    of the chain remains the same.



    Alkenes and cycloalkanes have two fewer hydrogen atoms than alkanes. That is

    why, they have the same molecular formula. However, they belong to different

    homologous series. Therefore, they are functional group isomers. This isomerism

    that relates open chain compounds to ring chain compounds is referred to as ring

    isomerism.



    2. Stereoisomerism

    Due to the impossibility of rotation around the double bond, alkenes give rise to

    cis-trans or geometrical isomerism.



    3.3. Preparation of alkenes



    Different methods are used for the preparation of alkenes. Most of them are

    elimination reactions.

    1. Dehydration of alcohols

    An alkene may be obtained by dehydration of an alcohol. The reaction involves

    the loss of H and OH (water) from adjacent carbons of an alcohol to form an  alkene. The dehydration is carried out by heating an alcohol with concentrated sulphuric acid or 85% phosphoric acid.


    If two or more alkenes may be obtained, the one having more substituents on

    the double bond generally predominates. This is the Zaitsev’s rule.


    This is due to the stability of the intermediate carbocation. The carbocation

    produced in step 2 may undergo a transposition (rearrangement) of a hydride ion

    or a methyl group giving a more stable carbocation and therefore a more stable

    alkene.


    Mechanism





    2. Dehydrohalogenation of halogenoalkanes

    alkenes. The reaction follows the Zaitsev’s rule.




    3. Dehalogenation of dihalogenoalkanes

    When a compound containing two halogen atoms on the adjacent carbon

    atoms is treated with magnesium or zinc it transforms to an alkene.




    3.4. Laboratory preparation and chemical test for ethene


    Activity 3.4

    Preparation of ethene Set up the apparatus as shown in the Figure below (Figure 3.1) and follow the instructions to perform the experiment on the preparation ofethane


    Requirements:

    Chemicals:

    Ethanol, aluminium oxide, lime water, mineral wool, bromine water,

    acidified potassium permanganate solution (very dilute), water.

    Additional apparatus:

    Boiling tube

    Rubber stopper with hole

    Delivery tube

    Trough

    Test- tube rack

    5 test tubes

    5 rubber stoppers for test tubes

    Spatula Procedure and setting

    Bunsen burner

    Glass rod

    Splint

    Matches 


    1. Preparation of ethene:

    - Pour some ethanol into the boiling tube to a 3 cm depth

    - Add some glass wool to soak up the ethanol, using a glass rod to push the wool

    down the tube.

     - Clamp the boiling tube in a horizontal position using a retort stand.

     - Put a small amount of aluminium oxide about half way along the boiling tube.

    - Complete the set up of the apparatus as shown in the diagram above.

    - Light the Bunsen burner, adjust it to a blue flame and heat the aluminium

    oxide. (Make sure the test tube is filled with water when you start to collect the

    gas produced.)

     - As the aluminium oxide gets hot the heat reaches the ethanol at the end of the

    tube. The ethanol then changes to vapour, passes over the hot aluminium oxide

    and is dehydrated to produce ethene gas.

    - Collect 5 test tubes of the gas and put a stopper on each tube when it is filled.

    - When the test tubes have all been filled, loosen the retort stand and raise the

    apparatus so that the delivery tube no longer dips into the water. This avoids

    suck back of water as the tube begins to cool which could cause the boiling

    tube to crack. Turn off the Bunsen burner. 


    2. Testing the properties of ethene

    Addition of bromine:

    - Taking great care, add about 1ml of the test tube of bromine water to one of

    the test tubes of ethene.

     - Replace the stopper and shake the tube a few times.

     - Record your observations.

    - Write down your conclusions 

    - Addition of acidified potassium permanganate:

    - Add about 1ml of very dilute potassium permanganate solution to one of the

    test tubes of ethene and shake the tube a few times.

     - Record your observations.

    - Write down your conclusions

     Combustion:

    - Remove the stopper of one of the tubes filled with ethene and apply a light to

    the mouth of the test tube using a lighted splint.

    - Allow the gas to burn and when it has stopped burning add a small amount of

    lime water to the test tube, stopper it and shake the tube a few times.

    - Write down your observations.


    Interpretation

    When ethanol is heated in the presence of aluminium oxide, a gas is produced. This

    gas does not react with lime water. This means that the produced gas is not carbon

    dioxide. The equation of the reaction is: 


    The gas decolourises bromine water. Bromine water is a test used to identify the

    presence of a carbon-carbon double bond or triple bond. The bromine adds across

    the double bond and a dibromoalkane is formed. The reaction between alkene and

    bromine water is shown below:


    If you shake an alkene with bromine water (or bubble a gaseous alkene through

    bromine water), the solution becomes colourless. Alkenes decolourise bromine

    water.

    The Figure 3.2 shows Bromine water added to ethene: before the reaction (left)

    the color of bromine appears, and after the reaction (right) the colour of bromine

    disappears.



    When ethene reacts with acidified potassium manganate (VII), the purple colour of

    the permanganate solution turned to colourless or light pink indicating the presence

    of the carbon – carbon double bond.The reaction is the following:



    The gas burns with a smoky flame producing carbon dioxide and heat energy. The

    carbon dioxide produced turns into milky lime water.



    3.5. Physical properties of alkenes


    Alkenes which have less than 5 carbon atoms are gaseous at ordinary

    temperature, the other are liquid up to 18 while others are solids as the

    number of carbon atoms increases.

    Boiling points and melting points of alkenes are less than those of alkanes

    but also increase as the molecular weight increase.

    Alkenes are insoluble in water but soluble in most organic solvents.

    Cis-alkenes have a slightly higher boiling point than the trans-isomers

    because the dipole moments in trans structures cancel each others----.




    3.6. Chemical properties

    3.6.1. Addition reactions
    3.6.1.1. Electrophilic additions




    Alkenes are far more reactive than alkanes due to the carbon-carbon double bond.

    These compounds are unsaturated and they can easily undergo addition reactions

    to yield saturated products.


    The double bond in alkenes is a region of high density of electrons. Therefore, this

    region is readily attacked by electrophiles. An electrophile is an atom, a molecule

    or an ion which is electron-deficient; i.e. it is a Lewis acid or an electron pair acceptor.




    1. Addition of hydrogen halides

    Hydrogen halides (HCl, HBr, HI) react with alkenes to yield halogenoalkanes. The

    reaction is carried out either with reagents in the gaseous state or in inert solvent

    such as tetrachloromathane. 



    When hydrogen halides add to unsymmetrical alkenes, the reaction leads to the

    formation of two products in two steps. The first step leads to the formation of

    two different carbocations with the major product formed from the more stable carbocation. This is the Markownikov’s rule. That is “The electrophilic addition of an unsymmetric reagent to an unsymmetric double bond proceeds by involving the most stable carbocation.




    2. Addition of water

    The hydration of alkenes catalysed by an acid is an electrophilic addition. Ethene

    can be transformed into ethanol. The first step consists of adding concentrated

    sulphuric acid. The second step consists of the hydrolysis of the product of the

    first step.

    In industry the reaction is carried out at approximately 300 °C in the prence of

    phosphoric acid as a catalyst.


    3. Addition of cold concentrated sulphuric acid

    When cold concentrated sulphuric acid reacts with alkene, an alkyl hydrogen

    sulphate is obtained. If the starting alkene is unsymmetrical, two different alkyl

    hydrogen sulphates are obtained. If the alkyl hydrogen sulphate is warmed in

    the presence of water, an alcohol is obtained.


    4. Addition of halogens

    The addition of halogens (halogenation) on alkenes yields vicinal

    dihalogenoalkanes. The reaction takes place with pure reagents or by mixing

    reagents in an inert organic solvent.

    When a chlorine or bromine molecule approaches an alkene, the pi electrons

    cloud interact with the halogen molecule causing its polarisation.




    3.6.1.2. Hydrogenation

    In the presence of a catalyst (Pt, Ni, Pd), alkenes react with hydrogen to give

    alkanes.


    Alkenes are readily oxidised due to the presence of the double bond.

    1. Reaction with oxygen

    i. Transformation to epoxides

    Ethene react with oxygen in the presence of silver as a catalyst to yield epoxyethane.




    3. Reaction with potassium permanganate

    Alkenes react with dilute potassium permanganate solution to give diols. The

    reaction takes place in the cold.

    The colour change depends on the medium of the reaction.





    4. Hydroformylation

    The hydroformylation is a process by which alkenes react with carbon monoxide

    and hydrogen in the presence of rhodium catalyst to give aldehydes.



    3.6.3. Addition polymerisation 



    Alkenes undergo addition polymerisation reaction to form long chain polymers.i.e

    a polymer is a large molecule containing a repeating unit derived from small unit

    called monomers. A polymerisation reaction involves joining together a large number of small molecules to form a large molecule.


    Many different addition polymers can be made from substituted ethene

    compounds.

    Each polymer has its physical properties and therefore many polymers have wide

    range of uses.

    Mechanism for the polymerisation of ethene.

    1. Initiation

    It is a free radical initiation.


    2. Propagation


    3. Termination 


    where the part between brackets indicates a unit of the formula of the polymer

    that repeats itself in the formula; n indicates the number of the units in a formula of

    a polymer and is a very large number.

    Summary of most alkene polymers obtained from alkenes as monomers and their

    uses (Table 3.1)





    3.7. Structure, classification and nomenclature of alkynes



    A triple bond consists of one sigma bond and two pi bonds. Each carbon of the triple

    bond uses two sp orbital to form sigma bonds with other atoms. The unhybridised 2p

    orbitals which are perpendicular to the axes of the two sp orbitals overlap sideways

    to form pi bonds.

    According to the VSEPR model, the molecular geometry in alkynes include bond

    angle of 180o around each carbon triply bonded.Thus, the shape around the triple

    bond is linear.


    There are two types of alkynes: terminal alkynes and non-terminal (internal)

    alkynes

    A terminal alkyne has a triple bond at the end of the chain e.g.: : R-C ≡ C − H

    A non-terminal alkyne has a triple bond in the middle of the chain: R − C ≡ C − R'

    Examples


    Alkynes are named by identifying the longest continuous chain containing the

    triple bond and changing the ending ane from the corresponding alkane to yne





    3.8. Laboratory and industrial preparation of alkynes

    1. Preparation of ethyne

    Activity: 3.8

    Set up the apparatus as shown in the diagram below. 




    Procedure:

    Place 2g of calcium carbide in a conical flask

    Using the dropping funnel, add water drop by drop.

    Collect the gas produced in the test tube.

    Remove the first tube and connect a second test tube.

    To the first test tube add two drops of bromine water. Record your observations

    To the second tube add two drops of potassium manganate (VII). Record your observations.


    Ethyne (acetylene) can be prepared from calcium carbide which is obtained by

    reduction of calcium oxide by coke at high temperature.



    When bromine water is added to acetylene, the red colour of bromine is discharged.

    The solution becomes colourless.

    The decolourisation of bromine water is a test for unsaturation in a compound.

    When potassium manganate (VII) is added to acetylene, its purple colour is

    discharged.

    2. Alkylation of acetylene

    The hydrogen atom of ethyne as that of other terminal alkynes is slightly acidic and therefore it can be removed by a strong base like NaNH2 or KNH2.The products of the reaction are acetylides. Acetylides react with halogenoalkanes to yield higher alkynes.


    3. Dehydrohalogenation

    The dehydrohalogenation of vicinal or geminal dihalogenoalkanes yields alkynes


    4. Dehalogenation

    The dehalogenation of a tetrahalogenoalkane yield an alkyne.


    3.9. Physical properties of alkynes


    Alkynes are non-polar compounds with physical properties similar to those of

    alkenes with the same number of carbon atoms. Their linear structure gives them

    greater intermolecular forces than alkenes




    3.10. Chemical reactions of alkynes


    Addition reactions

    As unsaturated hydrocarbons, alkynes are very reactive. Because they are unsaturated

    hydrocarbons, alkynes undergo addition reactions. Alkynes can add two moles of reagents.

    Even though they have a higher electron density than alkenes, they are in general less reactive because the triple bond is shorter and therefore the electron cloud is less accessible.

    1. Addition of hydrogen halides

    Alkynes react with hydrogen halides to yield vicinal dihalogenoalkanes, the reaction follows the Markownikov’s rule. The reaction takes place in four steps.


    2. Addition of water

    Alkynes react with water in the presence of sulphuric acid and mercury sulphate at 60o C to give carbonyl compounds.


    3. Hydrogenation

    The hydrogenation of alkynes in the presence of palladium catalyst gives alkanes

    The reaction requires two moles of hydrogen for a complete saturation.


    In the presence of Lindlar catalyst, the alkynes are partially hydrogenated giving alkenes4


    A Lindlar catalyst is a heterogeneous catalyst that consists of palladium deposited on

    calcium carbonate and poisoned with different lead derivatives such as lead oxide

    or lead acetate. A heterogeneous catalyst is the one which is in the phase different

    from that of the reactants.


    4. Reaction with metals

    Terminal alkynes react with active metals to yield alkynides and hydrogen gas.

    Internal alkynes do not react as they do not have an acidic hydrogen atom.



    5. Reaction with metal salts

    When a terminal alkyne is passed through a solution of ammoniacal silver nitrate, a white precipitate of silver carbide is formed.


    When a terminal alkyne is passed through a solution of ammoniacal copper(I)

    chloride, a red precipitate of copper(I)carbide is formed. 


    The reactions above are used to:

    Differentiate between terminal and non-terminal alkynes.

    Differentiate ethene and ethyne

    The reaction shows that hydrogen atoms of ethyne are slightly acidic, unlike those

    of ethene.



    3.11. Uses of alkenes and alkynes

    Activity 3.11

    Look at the picture below and appreciate the importance of alkenes and alkynes.




    Alkenes are extremely important in the manufacture of plastics which have

    many applications such as: packaging, wrapping, clothing, making clothes,

    artificial flowers, pipes, cups, windows, ...

    Ethene is a plant hormone involved in the ripening of fruits, seed germination,

    bud opening;


    Ethene derivatives are also used in the making of polymers such as polyvinylchloride (PVC), Teflon,...

    Alkenes are used as raw materials in industry for the manufacture of alcohols, aldehydes, ...

    Alkynes are used in the preparation of many other compounds. For exampleethyne is used in the making of ethanal, ethanoic acid, vinyl chloride, trichloroethane, ...

    Ethyne (acetylene) is used as a fuel in welding and cutting metals.

    Propyne is used as substitute for acetylene as fuel for welding.









    Activities: 0
  • UNIT 4: HALOGENOALKANES (ALKYL HALIDES)

    Key unit competency

    The learner should be able to relate the physical and chemical properties of halogenoalkanes to their reactivity and their uses

    Learning objectives

    Define halogenoalkanes and homologous series.

    Explain the reactivity of halogenoalkanes.

    Explain the physical properties of halogenoalkanes.

    Describe preparation methods for halogenoalkanes.

    Explain different mechanisms in halogenoalkanes.

    Explain the uses and dangers associated with halogenoalkanes.

    Draw displayed structural formulae of halogenoalkanes and give names

    using IUPAC system.

    Classify halogenoalkanes according to developed formula as primary,

    secondary and tertiary.

    Write reaction mechanisms of halogenoalkanes as SN1, SN2, E1 and E2.

    Test for the presence of halogenoalkanes in a given sample organic

    compound.

    Appreciate the uses and dangers of halogenoalkanes in everyday life.

    Develop the awareness in protecting the environment.

    Develop team work approach and confidence in group activities and

    presentation sessions.



    4.1. Definition and nomenclature of halogenoalkanes



    1. Definition

    Halogenoalkanes compounds are compounds in which the halogen atoms like

    chlorine, bromine, iodine or fluorine are attached to a hydrocarbon chain. When

    the halogen atom is attached to a hydrocarbon chain the compound is called a halogenoalkane or haloalkane or an alkyl halide

    Halogenoalkanes contain halogen atom(s) attached to the sp3 hybridised carbon atom of an alkyl group. 


    2. Nomenclature of halogenoalkanes

    Halogenoalkanes are organic compounds that contain a halogen atom: F, Cl, Br, I.

    They are named using the prefixes fluoro-, chloro-, bromo- and iodo-.

    Numbers are used if necessary to indicate the position of the halogen atom in the

    molecule.



    4.2. Classification and isomerism




    4.2.1. Classification of halogenoalkanes

    There are three types of halogenoalkanes:


    A primary halogenoalkane has a halogen atom attached to the ended carbon atom

    of the chain. A secondary halogenoalkane has a halogen atom attached to a carbon

    bonded to two other carbon atoms while a tertiary halogenoalkane has a halogen

    atom attached to a carbon bonded to three other carbon atoms.


    4.2.2. Isomerism

    Halogenoalkanes exhibit both chain and position isomerism.

    Example: Molecular formula C4H9Br

    a. Chain isomerism: This arises due to arrangement of carbon atoms in chains of

    different size.


    b. Position isomerism: This arises due to the different positions taken by the

    halogen atom on the same carbon chain.

    The following compounds are position isomers: CH3 CH2 CH2 CH2-Br and CH3 CH2 CH Br CH3; because the atoms of bromine are on different positions of the chain.

    Hence, all isomers of the compound with molecular formula C4H9 Br are the following.



    4.3. Physical properties of halogenoalkanes




    1. Volatility

    Volatility is a property that shows if a substance transforms easily or not into vapour

    or gaseous form. This property depends on the nature of the bonds that make up

    the molecule of the substance. Generally non polar covalent compounds are more

    volatile than polar covalent compounds. We know that halogens when bonded to

    other atoms form polar bonds because they possess high electronegativities: F =

    4.0, Cl = 3.0, Br = 2.8, I = 2.5, and C = 2.5.


    The more the difference of electronegativities of the atoms that form the bond,

    the more polar is the bond. This explains the high polarity of C-F bond with an

    electronegativity difference of 1.5, and the low polarity of C-Cl and C-Br bonds where

    the electronegativity differences are 0.5 and 0.3 respectively.

    The presence of polarity or charge distribution results into more attraction between

    polar molecules called dipole-dipole attraction forces, one type of Van der Waals

    forces, as shown below:


    The dashed line represents the attraction forces between the polar molecules or

    dipoles.


    Therefore, more energy must be supplied to separate polar molecules and this

    explains why melting and boiling temperatures of fluoroalkanes and chloroalkanes

    are higher than those of alkanes of similar molecular mass.


    As we have already learnt, molecules of organic halogen compounds are generally

    polar. Due to the greater polarity as well as higher molecular mass as compared

    to the parent hydrocarbons, the intermolecular forces of attraction (dipole-dipole

    and Van der Waals) are stronger in the halogen derivatives. That is why the boiling

    points of chlorides, bromides and iodides are considerably higher than those of the

    hydrocarbons of comparable molecular mass (Table 4.1).



    Chloromethane, bromomethane, chloroethane and some chlorofluoromethanes

    are gases at room temperature. Higher members are liquids or solids.


    The attractions get stronger as the molecules get bigger in size. The pattern of

    variation of boiling points of different halides is depicted in Figure 4.1. For the same

    alkyl group, the boiling points of alkyl halides increase in the order: RF <RCl < RBr, <

    RI This is because with the increase in size and mass of halogen atom, the magnitude of Van der waal forces increases.


    2. Solubility

    The solubility is the capacity of a substance to dissolve in a given solvent; in chemistry the most common solvent we refer to is water. It is a result of the interaction between the molecules of the substance, a solute, and the molecules of the solvent.

    Polar molecules can interact with water molecules, but the attractive forces set

    up between water molecules and molecules concerned are not as strong as the

    hydrogen bonds present in water. Halogenoalkanes therefore, although they

    dissolve more than alkanes, are only slightly soluble in water.

    3. State

    The state of matter is the physical appearance of that matter: solid, liquid and

    gaseous.

    Chloromethane, bromomethane, chloroethane and chloroethene are colourless

    gases at room temperature and pressure. The higher members are colourless

    liquids with a sweet pleasant smell

    4. Density

    The density is a measure of the quantity of matter by volume unit. Cotton wool is

    less dense than sand because if you compare the quantity of matter cotton wool

    and sand contained in for instance 1m3, you find that there more matter in sand than in cotton wool.

    The density of halogenoalkanes increases in the order RCl < RBr < RI, since the

    atomic weight of halogens increases in order Cl < Br < I. Iodo, bromo and polychloro

    derivatives are denser than water but chloro derivatives are less dense than water.




    4.4. Preparation methods of halogenoalkanes

    1. From alkenes and alkynes




    Direct halogenation of alkanes in the presence of ultraviolet light gives alkyl halides and a hydrogen halide.

























    Activities: 0
  • UNIT 5: ALCOHOLS AND ETHERS

    Key unit competency:
    To be able to compare the physical and chemical properties of alcohols and ethers to their preparation methods, reactivity and uses.

    Learning objectives:
    • Distinguish between alcohols from other organic compounds by representing the functional group of alcohols
    • Classify primary, secondary and tertiary alcohols by carrying out the method of identification
    • Write the name of alcohols by using IUPAC system
    • Describe the physical properties of alcohols to other series of organic compounds
    • Carry out the method of preparation of alcohols
    • Describe the local process of making alcohol by fermentation.
    • Explain the effect of oxidation on urwagwa when it overstays
    • Compare the physical, chemical and the method of preparation of alcohols to ethers
    • State the use of ethers

    5.1. Definition and nomenclature



    5.1.1. Definition
    Alcohols are organic compounds that are derivatives of hydrocarbons where one or more hydrogen atoms of hydrocarbon is or are replaced by hydroxyl (-OH) group. They are represented by the general formula: CnH2n+1OH or ROH where R is a radical: alkyl group made by a chain of carbon atoms

    Alcohols are called monohydric if only one hydroxyl group is present (eg: CH3CH2-OH). Dihydric alcohols are those with two hydroxyl group (diol: vicinal and gem), trihydric (triols) and polyhydric are those with many – C-OH groups. The functional group attached is –OH group to any atom of carbon.

    5.1.2. Nomenclature
    According to IUPAC system, alcohols are named by replacing the final ‘‘e’’ of the parent hydrocarbon with ‘‘ol’’, then specify the position of -OH group before ending by ol


    5.2. Classification and isomerism


    Alcohols are classified as:
    Primary alcohols: These have only one alkyl group attached to the carbon carrying the –OH.



    Functional isomers:
    Except methanol which has one carbon, other alcohols are isomers with ethers
    another chemical function of general formula R-O-R’ where R and R’are alkyl groups or aryl groups but not hydrogen.



    5.3. Physical properties



    a.Boiling points

    The chart shows the boiling points of some simple primary alcohols and alkanes with up to 4 carbon atoms.

    • The boiling point of an alcohol is always much higher than that of the alkane with the same number of carbon atoms.
    • The boiling points of the alcohols increase as the number of carbon atoms increases.
    • The boiling point of alcohols with branches is lower than that of unbranched alcohols with the same number of carbon atoms. This is because increased branching gives molecules a nearly spherical shape and the surface area of contact between molecules in the liquid. This results in weakened intermolecular forces and therefore in lower boiling points.
    • Tertiary alcohols exhibit the lowest boiling point than secondary and primary alcohols:
    • Primary alcohol                      > Secondary alcohol              > Tertiary alcohol
                                                    Highest boiling point                    lowest boiling point


    The patterns in boiling point reflect the patterns in intermolecular attractions: In the case of alcohols, there are hydrogen bonds set up between the slightly positive hydrogen atoms and lone pairs on oxygen in other molecules.



    b.Solubility of alcohols in water

    The lower members of alcohols are completely soluble in water because mixed hydrogen bonds between water and alcohol molecules are formed. As the length of hydrocarbon group of the alcohol increases, the solubility decreases.

    c. Volatility

    Alcohols are volatile and the volatility decreases as the molecular mass increases. Compared to alkyl halides, alcohols are less volatile. Polyalcohol are viscous or solids. Example: propane-1, 2, 3-triol (glycerine). This is due to stronger intermolecular forces than those of monoalcohols.


    5.4. Alcohol preparations


    b. From alkenes

    Alkenes react with water in the presence concentrated sulphuric acid to yields

    alcohols


    c. From carbonyl compounds

    When aldehydes and ketones are reduced by hydrogen in the presence of a

    suitable catalyst like Pt, Ni or Pd, they form primary and secondary alcohols

    respectively.





    d. From esters

    Esters on hydrolysis in the presence of mineral acid or alkalis produce alcohols and

    carboxylic acids.


    e. From Grignard reagents

    The reaction between carbonyl compound and Grignard reagent (alkyl magnesium

    halides) produces an alcohol with more carbon atoms. The reaction is a nucleophilic addition on a carbonyl compound.


    f. From primary amine to give primary alcohol

    Primary amines react with nitrous acid to produce primary alcohols.



    5.5. Preparation of ethanol by fermentation



    This method is mainly used to prepare ethanol industrially. Ethanol is prepared from starch
    (e.g. maize, cassava, millet, sorghum) and sugar(e.g. banana juice, molasses) by fermentation process.

    Fermentation can be defined as any of many anaerobic biochemical reactions in which enzymes produced by microorganisms catalyse the conversion of on substance into another.


    The ethanol obtained by fermentation process is only about 11%. This is made concentrated by distillation which converts it to about 95% ethanol. This on further distillation yields a constant boiling mixture whose composition does not change (an azeotropic mixture). Therefore, 100% ethanol is obtained by either:

    i. Adding quick lime which removes water
    ii. Distilling with of benzene as a third component
    Note: Methanol can be prepared industrially by the reaction of carbon monoxide
    and hydrogen at 300 °C and a pressure of 200 atmospheres.





    5.6.1. Oxidation 



    Aldehydes formed by oxidation of primary alcohols tend to undergo further oxidation to carboxylic acid.

    Ketones formed by oxidation of secondary alcohols are not further oxidised, unless if the oxidising agent is hot and concentrated in which case bonds around the –CO_ group are broken and two smaller carboxylic acids are formed.




    Tertiary alcohols resist oxidation because they have no hydrogen atom attached on the functional carbon atom. Oxidation also occurs when the alcohol is in gaseous phase by used of silver or copper catalyst under 500 °C and 300 °C respectively; and the vapour of the alcohol is passed with air (oxygen) over heated silver.


    An acidified potassium dichromate solution is turned from orange to green when it reacts with primary and secondary alcohols.

    Secondary alcohols having the following structure R-CHOH-CH3 only undergo oxidation, on treatment with iodine solution in the presence of sodium hydroxide to give yellow precipitate of tri-iodomethane.

    Note: This is a reaction which is characteristic of methyl ketones, CH3-CO-R’; but iodine here acting as an oxidizing agent first oxidizes the CH3-CHOH-R’toCH3-CO-R’ ; then the methyl ketone formed then gives the yellow precipitate of CHI3 (Iodoform). From the reaction involved we have the Iodoform test.


    5.6.2. Reaction with sulphuric acid











    5.6.4. Reaction with strong electropositive metals and metal hydroxides



    5.6.5 Action of hydrohalic acids (HX)




    Notice:
    i. Reaction with concentrated hydrochloric acid is catalyzed by anhydrous zinc chloride.

    ii. This reaction is called LUCAS test and is used to distinguish between simple primary, secondary or tertiary alcohols. In this reaction, the alcohol is shaken with a solution of zinc chloride in concentrated hydrochloric acid.

    Observations: Immediate cloudiness indicates presence of a tertiary alcohol. If the solution becomes cloudy within 5 minutes then the alcohol is a secondary one. Primary alcohol would show no cloudiness at room temperature since the reaction is very slow.

    For example all alcohols which are isomers of C4H10O can be distinguished by the LUCAS test.

    Alcohols are also transformed into halogenoalkanes using phosphorus halides and thionyl chloride.





    5.7. Uses of alcohols


    Ethanol is the alcohol found in alcoholic drinks. Alcoholic fermentation converts starch sugar into ethanol. For example grapes are used to produce wine, ripe banana to produce urwagwa, honey for spirits are obtained by distilling the ethanol –water product obtained when sugar is fermented.

    Drinking alcohol, i.e. the ethylic alcohol also called ethanol, is a normal social activity; but excess of it is dangerous for our health. Hence excess of alcoholic consumption must be avoided.For non-adult youth, consumption of alcohol in any form is illegal in Rwanda and many other countries.

    There are some alcoholic drinks produced in Rwanda and in the Region that are prohibited to be sold in Rwanda. However, alcohols have many other applications in daily life as indicated in the Table 5.1.



    Ethanol produced by sugar cane fermentation has been used as alternative fuel to gasoline (petrol). It has been mixed with gasoline to produce gasohol.




    1. Ethers are sparingly soluble in water but are soluble in organic solvents.
    2. The polar nature of the C-O bond (due to the electronegativity difference of the atoms) results in intermolecular dipole-dipole interactions.
    3. An ether cannot form hydrogen bonds with other ether molecules since there is no H to be donated (no -OH group).
    4. Their melting and boiling points increase with the increase in molecular mass because of increasing the magnitude of Van der Waal’s forces with size.
    5. The boiling points of ethers are much lower than those of alcohols of similar molecular mass. This is because of the intermolecular hydrogen bonding which are present in alcohols but are not possible in ethers.




    Since they are saturated compounds and non-polar, they are relatively chemically inert reason why their chemical reactions are very few.



    a. Ethers can act as the Lewis base due to the two non-bonded electron pair on oxygen to form coordinative bonds with Grignard reagent. This explains clearly why organ magnesium compounds are manipulated in ether solvent but not in water since in water, there is a reaction which generate alkanes.




    Lower ethers are used as anesthesia since they produce inert local cooling when sprayed on a skin, ether are also used as local anesthesia for minor surgery operation.Lower ethers are volatile liquid which on evaporation produce low temperature they are therefore used as refrigerants.

    Ether itself is one of the most important organic solvents for fats, oils, resins, and alkaloids.


    Activities: 0
  • UNIT 6: CARBONYL COMPOUNDS: ALDEHYDES AND KETONES

    Key unit competency

    To be able to compare the chemical nature of carbonyl compounds to their

    reactivity and uses.

    Learning objectives

    Describe the reactivity of carbonyl compounds

    State the physical properties of aldehydes and ketones

    Describe the preparation reactions of ketones and aldehydes

    Explain the mechanism of nucleophilic addition reactions of carbonyl

    compounds

    Prepare ketones from secondary alcohols by oxidation reactions

    Compare aldehydes and ketones by using Fehling’s solution and Tollens’

    reagent

    Write and name carbonyl compounds and isomers of ketones and aldehydes

    Write equations for the reactions of carbonyl compounds with other

    substances

    Compare the physical properties of carbonyl compounds to those of alcohols

    and alkenes

    Differentiate the methyl ketones from other ketones by using the iodoform

    test

    Carry out an experiment to distinguish between carbonyl compounds and

    other organic compounds

    Carry out an experiment to distinguish between ketones and aldehydes

    Carry out an experiment to prepare ethanol and propan-2-one.


    6.1. Definition and nomenclature of carbonyl compounds


    Introductory activity

    Many fruits such as mangoes and honey contained sugar.The following images

    represent mangoes, honey and some sugars such as fructose and glucose. 


    6.1.1 Definition



    Carbonyl compounds are compounds that contain carbon-oxygen double bond

    (C=O). Carbonyl compounds are classified into two general categories based on the

    kinds of chemistry they undergo. In one category there are aldehydes and ketones;

    in the other category there are carboxylic acids and their derivatives. This unit looks

    on category of aldehydes and ketones.


    Aldehyde molecules

    For aldehydes, the carbonyl group is attached to hydrogen atom and alkyl group as

    shown in the molecule of propanal below. Methanal is the smallest aldehyde, it has

    two hydrogen atoms attached to carbonyl group.


    If you are going to write this in a condensed form, you write aldehyde as –CHO,

    don’t write it as -COH, because that looks like an alcohol functional group.


    Ketone molecules



    6.1.2 Nomenclature

    Aldehydes


    The systematic name of an aldehyde is obtained by replacing the terminal “e” from

    the name of the parent hydrocarbon with “al.”In numbering the carbon chain of an

    aldehyde, the carbonyl carbon is numbered one.



    Ketones

    The systematic name of a ketone is obtained by removing the terminal“e” from the

    name of the parent hydrocarbon and adding “one.”The chain is numbered in the

    direction that gives the carbonyl carbon the smallest number.Ketone contains

    a carbon-oxygen double bond just like aldehyde, but for ketone carbonyl groupis

    bonded to two alkyl groups. 




    6.2. Isomerism



    6.2.1 Functional isomerism in aldehydes and ketones


    Isomers are molecules that have the same molecular formula, but have a different

    arrangement of the atoms in space. Functional group isomers are molecules that

    have same molecular formula but contain different functional groups, and they

    belong to different homologous series of compounds.



    6.2.2. Position isomerism in ketones 

    Position isomerism is isomerism where carbon skeleton remains constant, but the

    functional group takes different positions on carbon skeleton.



    6.2.3. Chain isomerism in aldehydes and ketones

    In chain isomerism the same number of carbons forms different skeletons.

    Aldehydes with 4 or more carbon atoms and ketones with five or more carbon

    atoms show chain isomerism. 



    6.3. Physical properties of aldehydes and ketones


    6.3.1. Solubility in water aldehydes and ketones


    The small molecules of aldehydes and ketones are soluble in water but solubility

    decreases with increase of carbon chain. Methanal, ethanal and propanone - the

    common small aldehydes and ketones are soluble in water at all proportions.

    Even though aldehydes and ketones don’t form hydrogen bond with themselves,

    they can form hydrogen bond with water molecules.


    The slightly positive hydrogen atoms in a water molecule can be sufficiently

    attracted to the lone pair on the oxygen atom of an aldehyde or ketone to form a

    hydrogen bond.


    Other intermolecular forces present between the molecules of aldehyde or ketone

    and the water are dispersion forces and dipole-dipole attractions

    Forming these attractions releases energy which helps to supply the energy

    needed to separate the water molecules and aldehyde or ketone molecules from

    each other before they can mix together.


    Apart from the carbonyl group, hydrocarbon chains are non polar, they don’t

    dissolve in water. By forcing hydrocarbon chain to mix with water molecules, they

    break the relatively strong hydrogen bonds between water molecules without

    replacing them by other attractions good like hydrogen bonds. This makes the

    process energetically less profitable, and so solubility decrease.


    6.3.2. Boiling points of aldehydes and the ketones


    Methanal is a gas and has a boiling point of -21°C, and ethanal has a boiling point

    of +21°C. The other aldehydes and ketones are liquids or solids, with boiling points

    rising with rising of molecular mass hence rising of strength of Van der Waals force. 


    Comparing the physical properties of carbonyl compounds to those of alcohols

    and alkanes


    Physical properties of covalent compounds depend on intermolecular forces.

    Compounds that have similar molecular mass but different intermolecular forces

    have different physical properties.


    Alcohols have higher boiling point than aldehydes and ketones of similar lengths. In

    the alcohol, there is hydrogen bonding, but the molecules of aldehydes and ketones

    don’t form hydrogen bonds.Aldehydes and ketones are polar molecules but alkanes

    are non polar molecules. 



    6.4. Chemical properties of carbonyl compounds

    6.4.1. Nucleophilic addition reactions



    a. Polarity of carbonyl group

    By comparing carbon-carbon double bond and carbon- oxygen double bond

    the only difference between bonds C=C and C=O is distribution of electrons. The

    distribution of electrons in the pi bond is heavily attracted towards the oxygen atom,

    because oxygen atom is much more electronegative than carbon.


    During chemical reactions nucleophiles will attack carbon of the carbonyl functional

    group which bears apartial positive charge. While electrophile will attack oxygen of

    the carbonyl functional group which bears a partial negative charge.


    b. Reaction of HCN with aldehydes and ketones

    Hydrogen cyanide adds to aldehydes or ketones to form cyanohydrins or

    hydroxynitriles.The product has one more carbon atom than the reactant. For

    example, ethanal reacts with HCN to form 2-hydroxypropanenitrile:



    Because hydrogen cyanide is a toxic gas, the best way to carry out this reaction is to

    generate hydrogen cyanide during the reaction by adding HCl to a mixture of the

    aldehyde or ketone and excess sodium cyanide. Excess sodium cyanide is used in

    order to make sure that some cyanide ion is available to act as a nucleophile. The

    solution will contain hydrogen cyanide (from the reaction between the sodium or

    potassium cyanide and the HCl)

    The pH of the solution is maintained in range 4 - 5, because this gives the fastest

    reaction. The reaction takes place at room temperature.


    c. The mechanism of reaction between HCN and propanone



    d. Application of the reaction

    The product of the reaction above has two functional groups:

    The -OH group which behaves like ordinary alcohol and can be replaced by

    other substituent like chlorine, which can in turn be replaced to give other

    functional group, for example, an -NH2

     group;

    The -CN group which can be hydrolysed into a carboxylic acid functional

    group -COOH.



    e.Reaction of NaHSO3 with aldehydes or ketones

    The aldehyde or ketone is shaken with a saturated solution of sodium hydrogen

    sulphite in water. Hydrogen sulphite with negative charge act as nucleophile,

    where the product formed is separated as white crystals. Propanone react hydrogen

    sulphite, as below:


    Impure aldehyde and ketone can be purified by using this reaction. Impure

    aldehyde or ketone is shaken with a saturated solution of sodium hydrogensulphite

    to produce the crystals. Impurities don’t form crystals; these crystals formed are

    filtered and washed to remove any impurities. Addition of dilute acid to filtered

    crystals regenerates the original aldehyde. Dilute alkali also can be added instead

    dilute acid. 




    6.4.2. Condensation reactions



    a. Experimental reaction

    The procedure of the preparation of Brady’s reagent and carbonyl compounds

    changesslightly depending on the nature of the aldehyde or ketone, and the solvent

    in which 2,4-dinitrophenylhydrazine is dissolved in. The Brady’s reagent for activities

    (6.4.1) is a solution of the 2,4-dinitrophenylhydrazine in methanol and sulphuric acid.


    Add a few drops of Brady’s reagent to either aldehyde or ketone. A bright orange or

    yellow precipitate indicates the presence of the carbonyl group in an aldehyde or

    ketone. 


    b. Structural formula of 2,4-dinitrophenylhydrazine.

    The carbon of benzene attached to hydrazine is counted as number one.In

    2,4-dinitrophenylhydrazine, there are two nitro groups, NO2,attached to the phenyl

    group in the 2- and 4- positions.



    c. The reaction of carbonyl compounds with 2,4-dinitrophenylhydrazine

    Brady’s reagent is a solution of the 2,4-dinitrophenylhydrazine in methanol

    and sulphuric acid. The overall reaction of carbonyl compounds with

    2,4-dinitrophenylhydrazine is:



    Where R and R’ represent alkyl groups or hydrogen(s); if both or only one is hydrogens

    the starting carbonyl compound is an aldehyde. If both R and R’ are alkyl groups

    the carbonyl compound is a ketone. The following molecule shows clearly how the

    product is formed.



    The product formed is named”2,4-dinitrophenylhydrazone”. The simple difference

    consists in replacing suffix “-ine” by “-one”.

    The reaction of 2,4-dinitrophenylhydrazine with ethanal produces ethanal

    2,4-dinitrophenylhydrazone; The reaction of 2,4-dinitrophenylhydrazine with

    butanal produces butanal 2,4-dinitrophenylhydrazone. This is an example of

    condensation reaction.

    During the chemical reaction, the change takes place only on nitrogen (-NH2) of

    hydrazine in 2,4-dinitrophenylhydrazine. If the -NH2 group is attached to other

    groups a similar reaction as that of 2,4-dinitrophenylhydrazine will take place: 




    6.4.3. Oxidation reactions using KMnO4/H+ and K2Cr2O7/H+



    a. Difference in reactivity of ketones and aldehydes with K2Cr2O7


    By considering the structural formulae of aldehydes and ketones, the difference is

    only the presence of a hydrogen atom attached to the carbonyl functional group in

    the aldehyde whereas ketones have a alkyl group instead.



    During chemical reaction aldehydes react with oxidizing agent; hydrogen on

    carbonyl functional group is replaced by oxygen, look on figure below. The presence

    of hydrogen atom makes aldehydes very easy to oxidize, in other words aldehydes

    are strong reducing agents.


    For ketone, absence of hydrogen on carbonyl functional group makes ketones to

    resist oxidation. But very strong oxidising agents like potassium permanganate

    solution oxidize ketones - and they do it in a destructive way, by breaking carboncarbon bonds.


    Aldehyde oxidation can take place in acidic or alkaline solutions. Under acidic

    solutions, the aldehyde is oxidized to a carboxylic acid. Under alkaline solutions, acid

    formed react with base to form a salt of carboxylic acid. 



    b. Oxidation of aldehyde by K2Cr2O7/H+ solution


    Add few drops of the aldehyde or ketone to a solution of potassium dichromate

    (VI) acidified with dilute sulphuric acid. If the color doesn’t change in the cold, the

    mixture is warmed gently in a beaker containing hot water.


    6.4.4. Oxidation reactions using Tollens’ reagent


    a. Difference in reactivity of Ketones and Aldehydes with Tollens’ reagent

    Aldehydes can also be oxidized into carboxylic ions in basic medium.Tollens’ reagent

    is a solution of diamminesilver (I) ion, [Ag(NH3)2]+ and OH-.In order to identify if a

    substance is aldehyde or ketone, add few drops of Tollens reagent to test tubes

    containing aldehyde or ketone and warm gently in a hot water bath for a few minutes. The formations of sliver mirror or grey precipitate is an indication of the presence of aldehyde.



    6.4.5. Oxidation reactions using Fehling ;or Benedict; solution



    a. Difference in reactivity of Ketones and Aldehydes with Fehling or Benedict

    solution.

    Fehling’s solution and Benedict’s solution react with aldehyde in the same way; both

    solutions contain Cu2+ and OH. In Fehling’s solution Cu2+ is complexed with tartrate

    ligand butin Benedict’s solution Cu2+ is complexed with citrate ligand.


    Don’t worry about ligands, important reagents are Cu2+ and OH, ligands tartrate and

    citrate are used to prevent formation of precipitate copper (II) hydroxide or copper

    (II) carbonate.


    A few drops of Fehling’s solution or Benedict’s solution is added to the aldehyde or

    ketone and the mixture is warmed gently in a hot water bath for a few minutes.





    6.4.6. Iodoform reaction with aldehydes and ketones

    Activity 6.4.6

    Materials:



    a. Reagents for iodoform reaction

    There are two different mixtures that can be used to do iodoform test, these

    mixture are:

    Iodine and sodium hydroxide solution

    Potassium iodide and sodium chlorate (I) solutions

    Don’t worry about Potassium iodide and sodium chlorate(I) solutions, Potassium

    iodide and sodium chlorate(I) react to form final solution containIand OH-. Both mixtures contain the same reagents.

    Each of these mixtures contains important reagent Iand OHwhich react with

    aldehyde or ketone. When I2 and OH is added to a carbonyl compound containing the group CHCO (blue in the cycle) as shown below, pale yellow precipitate (triiodomethane) is formed.



    a. Description of iodoform test

    For iodine and sodium hydroxide solution

    Iodine solution, I3- , is added to aldehyde or ketone, followed by just enough sodium

    hydroxide solution to remove the colour of the iodine. If pale yellow precipitate

    doesn’t form in the cold, it may be necessary to warm the mixture very gently. The positive result is pale yellow precipitate of CHI3 


    For potassium iodide and sodium chlorate (I) solutions

    Potassium iodide solution is added to a small amount of aldehyde or ketone, followed

    by sodium chlorate (I) solution. If pale yellow precipitate doesn’t form in the cold,

    warm the mixture very gently. The positive result is pale yellow precipitate of CHI3.


    Reaction of iodoform test

    The reagents of iodoform test are I2 and OHsolution. The reaction takes place into

    two main steps:

    Three hydroxides, OH- , remove three hydrogens from methyl group and the

    place of hydrogen is taken by iodide.




    6.5. Preparation methods of aldehydes and ketones

    6.5.1. Oxidation of alcohols 



    a. alcohol by K2\Cr2O7/H+

    Potassium dichromate (VI) acidified with dilute sulphuric acid is used as oxidizing agent during the preparation of aldehyde or ketone. Primary alcohol is oxidized to  aldehyde, oxygen atom from the oxidising agent removes two hydrogens; one from the -OH group of the alcohol and the other hydrogen comes from the carbon that is attached to hydroxide functional group .




    b.Technique of stopping oxidation of aldehyde

    The aldehyde produced by oxidation of alcohol could make further oxidation to a

    carboxylic acid if the acidified potassium dichromate (VI) is still present in solution

    where reaction takes place. In order to prevent this further oxidation of aldehyde to

    carboxylic the following technique are used.

    Use an excess of the alcohol than potassium dichromate (VI). Potassium

    dichromate (VI) is limiting reactant hence there isn’t enough oxidising agent

    present to carry out the second stage of oxidizing the aldehyde formed to a

    carboxylic acid.

    Distil off the aldehyde as soon as it forms. Removing the aldehyde as soon as it

    is formed this means that aldehyde is removed from solution where oxidizing

    agent is, to prevent further oxidation. Ethanol produces ethanal as shown by

    the following reaction.




    c. Oxidation of alkene by KMnO4/H+




    6.5.2. Preparation of ketone by distillation of calcium acetate


    Procedure: Transfer 15g of calcium acetate in 50ml round bottom flask fixed on

    a stand, and place it on a heating mantle fitted with a condenser and a receiver

    flask. Adjust the temperature until the condensation starts. Use the aluminium

    foil to insulate the flask. Heat the flask and collect the acetone in receiver flask. The

    obtained product is a crude acetone and needs to be purified.Set up a distillation

    apparatus and distil the crude product to obtain pure acetone (56Oc). Do not forget

    to use stirrer bar which must be placed in the round bottom flask containing the

    acetone.


    6.6. Uses of aldehydes and ketones

    Aldehydes and ketones have many uses for example in industries such as

    pharmaceutical industry and in medicine.


    a. Formaldehyde:

    Formaldehyde is a gas at room temperature but is sold as a 37 percent solution in water.

    Formaldehyde is used as preservative and germicide, fungicide, and insecticide

    for plants and vegetables. Formaldehyde is mainly used in production of certain

    polymers like Bakelite (Figure 6.1). Bakelite and formaldehyde is used as

    monomers in production of Bakelite


    b. Acetone as solvent: 

    Acetone  is soluble in water at all proportions and also dissolves in many organic

    compounds. Boiling point of acetone is low, 56 °C, which makes it easier to be removed by

    evaporation. Acetone is an industrial solvent that is used in products such as paints,

    varnishes, resins, coatings, and nail polish removers.


    c. Aldehydes and ketones

    Organic molecules that contain ketones or aldehydes functional group are found

    in different foods such as irish potatoes, yellow bananas.

    Aldehydes and ketones perform essential functions in humans and other living organisms. For examples sugars, starch, and cellulose, which are formed from simple molecules that have aldehyde or ketone functional group

    d. Aldehydes and ketones in human’s body



    Aldehydes and ketones functional group are found in humans hormones like progesterone,

    testosterone. 






    Activities: 0
  • UNIT 7: CARBOXYLIC ACIDS AND ACYL CHLORIDES

    Key unit competency:

    The learner should be able to compare the chemical nature of the carboxylic acids

    and acid halides to their reactivity.

    Learning objectives

    Explain the physical properties and uses of carboxylic acids and acyl chlorides

    Describe the inductive effect on the acidity of carboxylic acid

    Explain the reactions of carboxylic acids and acyl chlorides

    Apply the IUPAC rules to name different carboxylic acids acyl chlorides

    Write the structural formula and isomers of carboxylic acids

    Distinguish between carboxylic acids from other organic compounds using

    appropriate chemical test

    Prepare carboxylic acids from oxidation of aldehydes or primary alcohols

    Compare the physical properties of carboxylic acids to those of alcohols

    Outline the mechanisms of esterification and those of reaction of acyl

    chlorides with ammonia , amines and alcohols

    Develop a culture of working as a team group activities and self-confidence

    in presentation

    Appreciate the uses of carboxylic acids as the intermediate compounds in

    industrial processes such as aspirin, vinegar and perfumes


    Carboxylic acid is classified in the family of organic compounds due to the presence

    of carboxyl group (-COOH) in their chemical formula. The general formula for

    carboxylic acids is R-COOH where R- refers to the alkyl group of the molecule.




    7.1.1. Nomenclature


    Carboxylic acids are named by following the general rules of naming organic

    compounds, where the suffix ‘oic acid’ is added to the stem name of the longest

    carbon chain that contains the acid functional group. The side branches are also

    positioned by starting from the carbon with carboxylic functional group.

    The carboxylic group takes priority to other functional group when numbering

    carbons in thecase of substituted chain.





    • Optical isomers

    Optical isomers have the same molecular formula and the same structural formula,

    but they are different in the spatial arrangement of atoms and their optical properties.

    An organic compound shows optical isomerism, when there is chiral carbon (a

    carbon atom attached to four diverse groups) in its structure. A chiral carbon is also

    known as asymmetric carbon



    Just as the right hand and left hand are mirror images of another but not superimposable, optical isomers, also known as enantiomers, are different from each other and can have different properties. For example, muscles produce D-lactic acid when they contract, and a high amount of this compound in muscles causes muscular pain and cramps.

    These molecules are optical isomers, because they have opposite optical activities.They can be distinguished by a plane-polarized light where one enantiomer rotates the light to the right while the other rotates it to the left.

    Enantiomers are often identified as D- or L- prefixes because of the direction in which

    they rotate the plane polarized light as shown in figures 7.2 and 7.3. Enantiomers

    that rotate plane polarized light in clockwise direction are known as dextrorotatory

    (right-handed) molecules and enantiomers that rotate plane polarized light in

    anticlockwise direction are known as levorotatory (left-handed) molecules.


    A solution containing equal amounts of enantiomers, 50% levorotatory and 50%

    dextrorotatory is known as a racemic mixture that will not rotate polarized light,

    because the rotations of the two enantiomers cancel each other out. 




    7.2. Physical properties of carboxylic acids



    a. Physical state

    Many carboxylic acids are colorless liquids with disagreeable odors. Aliphatic

    carboxylic acids with 5 to 10 carbon atoms are all liquids with a “goaty” odors (odor

    of cheese). These acids are also produced by the action of skin bacteria on human

    sebum (skin oils), which accounts for the odor of poorly ventilated storerooms.

    The acids with more than 10 carbon atoms are wax-like solids, and their odor

    diminishes with increasing molar mass and resultant decreasing volatility.

    Anhydrous acetic acid freezes at (17oC) slightly below ordinary room temperature,

    reason why it is called glacial acetic acid (Figure 7.4). But a mixture of acetic acid

    with water solidifies at much lower temperature.



    b. Melting and boiling point

    Carboxylic acids show a high degree of association through hydrogen bonding.

    Because of this, they have high melting and boiling points compared to other

    organic compounds of the same mass or number of carbon atoms.



    Carboxylic acids have high melting and boiling points because their hydrogen

    bonds enhance the possibility of bringing two acid molecules together by forming

    a kind of dimer.





    7.3. Acidity of carboxylic acids




    Solutions of carboxylic acid turn blue litmus paper red; they do not change the

    color of red litmus paper; therefore, they are acids as other mineral acids such as

    HCl (aq).

    Organic or carboxylic acids are weak acids in opposition to some mineral acids such

    as hydrochloric acids which are strong acids.According to Arrhenius’ theory of acids

    and bases, strong acids dissociate completely in water to give hydrogen ion, H+(aq) or

    H3O+, whereas weak acids dissociate partially. The hydrogen ion released combines with a water molecule to form H3O+ a hydrate positive ion called hydronium H3O+:


    The carboxylate ion formed by ionization of the acid is more stable than the acid

    because it has many resonance structures.


    Ethanoic acid is a weaker acid than methanoic because its methyl group has a

    positive inductive effect; that is to mean that it pushes electrons towards the O-H

    bond hence make hydrogen ion stable and not easily leaving.



    The greater the number of such groups, the greater the effected and therefore

    the weaker will be the acid.For example, 2,2-dimethylpropanoic is weaker than

    2-methylpropanoic acid which is in turn weaker than propanoic.


    The same rule applies to the increase in the length of the alkyl group chain.Butanoic

    acid is a weaker acid than propanoic acid which shows that the acidity strength

    decreases as the alkyl chain increases.


    On the other hand, when an electron withdrawing group (a group with a negative

    inductive effect) is present, the opposite effect is observed. For example,

    chloroethanoic acid is a stronger acid than ethanoic acid. This is because chlorine

    being electronegative, will withdraw electron towards itself thus reducing the

    electron density around the O-H bond thus weakening it. It causes O-H bond to

    easily break, and the concentration of hydrogen ions will be high in the solution.




    The more the number of groups with negative inductive effect, the greater is the

    effect and hence the more acidic will be the solution. Trifluoroacetic acid is more

    acidic than trichloroacetic, dichloroacetic, chloroacetic and acetic acid because

    fluorine is more electronegative than chlorine and hydrogen. It will strongly

    withdraw electron towards itself, hence makes easier for the proton to leave.It must

    also be noted that the further away the electronegative element, the less the effect.

    For example, 3-chlorobutanoic acid is therefore a weaker acid than 2-chlorobutanoic

    acid.




    7.4. Preparation of carboxylic acids




    Carboxylic acids are common and vital functional group; found in amino acids,

    fatty acids etc. and provide the starting raw material for acid derivatives such as

    acyl chlorides, amides, esters and acid anhydrides. There are several methods

    of preparation of carboxylic acids where the most common are discussed in this

    section.


    7.4.1. From primary alcohols and aldehydes


    Different carboxylic acids can be prepared by oxidation of either primary alcohols

    or aldehydes. In the process, the mixture of alcohol is heated under reflux with an

    oxidizing agent such acidified potassium permanganate or potassium dichromate.

    Primary alcohols are first oxidized to aldehydes then further oxidation of aldehydes

    produces carboxylic acid.



    7.4.2. Hydrolysis of acid nitriles and amides with acid or alkali

    When nitriles are hydrolyzed by water in acidic medium and the mixture is submitted

    to heat, the reaction yields carboxylic acids.




    7.4.3. From dicarboxylic acid

    Monocarboxylic acids can be prepared by heatingcarboxylic acids which have two

    carboxylic functional groups attached to the same carbon atom.


    Note that the reaction is used to reduce length of the carbon chain. The mono

    carboxylic acid prepared has one carbon atom less than the starting dicarboxylic

    acid.

    7.4.4. From organomagnesium compounds (Carboxylation reaction)

    Grignard reagents react with carbon dioxide gas, and when the intermediate compound formed is hydrolyzed it finally forms carboxylic acid.


    Mechanism:



    7.4.5. From alkenes (Oxidation of alkenes)

    Carboxylic acids are also obtained by heating alkenes with concentrated acidified

    potassium permanganate. The reaction unfortunately forms a mixture of compounds

    that mustbe later separated.


    Note that the hydrolysis of carboxylic acid derivatives such as amide, esters, acyl

    chloride and acid anhydrides also produce the corresponding acids.

    7.4.6. Laboratory preparation of acetic acid




    7.5. Reactions of carboxylic acids







    The reaction of acids with carbonates is the basis for the chemical test of carboxylic

    acid functional group and it can be used to distinguish carboxylic acids from other

    functional groups in qualitative analysis.

    Carbon dioxide produced is also tested by lime water and it turns lime water milky

    (Figure 7.8)



    It is noted that the oxygen atom in the ester formed comes from the alcohol and the

    one in water is from the acid. In the mechanism of esterification, the acid loses -OH

    group while the alcohol loses H-atom.




    7.5.3. Reduction of carboxylic acids

    Carboxylic acids are reduced to primary alcohols on treatment with reducing agent

    such as LiAlH4 in dry ether or by use of hydrogen in the presence of Ni catalyst. The

    reduction does not form aldehyde as an intermediate product, like in oxidation of

    primary alcohols.






    7.6. Uses of carboxylic acids




    Food industry and nutrition

    Food additives: Sorbic acid, benzoic acid, etc.

    Main ingredient of common vinegar (acetic acid).

    Elaboration of cheese and other milk products (lactic acid).

    Pharmaceutical industry

    Antipyretic and analgesic (acetylsalicylic acid or aspirin).

    Active in the process of synthesis of aromas, in some drugs (butyric or butanoic acid).

    Antimycotic and fungicide (Caprylic acid and benzoic acid combined with salicylic acid).

    Active for the manufacture of medicines based on vitamin C (ascorbic acid).

    Manufacture of some laxatives (Hydroxybutanedioic acid).


     Other industries

    Manufacture of varnishes, resins and transparent adhesives (acrylic acid).

    Manufacture of paints and varnishes (Linoleic acid).

    Manufacture of soaps, detergents, shampoos, cosmetics and metal cleaning products (Oleic acid).

    Manufacture of toothpaste (Salicylic acid).

    Production of dyes and tanned leather (Methanoic acid).

    Manufacture of rubber (Acetic acid).

    Preparation of paraffin candles (Stearic acid)


    7.7. Acyl chlorides and nomenclature 


    Acyl halides are compounds with the general formula where the–OH group of

    carboxylic acid has been substituted by a halogen atom. The acyl remaining

    structure is represented as:


    Their isomers can be chain isomerism, positional isomerism and functional isomerism

    with chloro aldehydes and ketones, alcohols with double bond C=C and chlorine as

    a substituent, cyclic ethers with chlorine.


    Acid chlorides have not many applications in our everyday life, but industrially they

    are used in synthesis of perfumes and nylons, which are polymers of high importance

    in textile industry. They can also be used in pharmaceutical industries to synthesize

    drugs with aromatic ester or amide functional groups like aspirin or paracetamol.




    7.7.1. Physical properties



    Appearance

    Acyl chlorides are colourless fuming liquids. Their characteristic strong smell is

    caused by hydrogen chloride gas that is produced when they get in contact with

    moisture (see figure 7.7). For example, the strong smell of ethanoyl chloride is a

    mixture of vinegar odour and the acrid smell of hydrogen chloride gas.


    b. Solubility

    Acyl chlorides are slightly soluble in water due to their small dipole that can interact

    with the polarity of water molecule. They cannot be said to be soluble in water

    because they readily react with water. It is impossible to have a simple aqueous

    solution of acyl chlorides, rather we have the products of their reaction with water.


    c. Boiling and melting points

    Acyl chloride molecules interact by Van der Waals forces whose strength increases

    with the increase in molecular masses of the compounds. 


    The boiling and melting points of acyl chlorides increases as their molecular masses

    rise. They have lower boiling and melting points than alcohols and carboxylic acids

    of the same number of carbon atoms, because they lack hydrogen bonds.


    7.7.2. Reactions of acyl chlorides


    The chemistry of acyl chlorides is dominated by nucleophilic substitution, where

    a stronger nucleophile replaces chlorine atom of acyl chloride. They undergo

    nucleophilic substitution reactions more easily than alkyl halides and carboxylic

    acids because the nucleophile targets the carbon which is deficient in electrons and

    -Cl is better leaving group than -OH group.


    The common reactions of acyl chlorides include reactions with water, alcohols and

    ammonia and amines. These reactants have a very electronegative element that

    has a free lone pair of electrons to act as a nucleophile.




    Reaction with alcohols

    They react with alcohol to produce esters with high yields than esterification of an

    alcohol and carboxylic acid, since Cl-atom in acyl chloride is a better leaving group

    than O-H for the case of carboxylic acid. The difference in electronegativity is the

    main reason for this observation.



    Reaction with ammonia and amine


    Acyl chlorides react with ammonia and amines to yield amides. Ammonia, primary

    amines and secondary amines form primary amides, secondary amides and tertiary

    amides respectively.










    Activities: 0
  • UNIT 8: ESTERS, ACID ANHYDRIDES, AMIDES AND ITRILES.

    Key unit competency:

    To be able to relate the functional groups of esters, acid anhydrides, amides and

    nitriles to their reactivity, preparation methods and uses. 



    8.1. Structure and nomenclature of esters 

    8.1.1. Structure of esters

    In unit 7, the reactions of carboxylic acids were discussed. The reactions of carboxylic acids produce the derivatives of acids such as esters, acid halides, acid anhydrides and amides.

    The general molecular formula of esters is Cn H2nO2  and their general structural

    formula is: RCOOR’ or




    Esters are known for their distinctive odor and they are commonly responsible for

    the characteristic of food (fruits) aroma, flowers and fragrances. Esters are found in

    nature but they can be also synthesized. Both natural and synthetic esters are used

    in perfumes and as flavoring agents.

    8.1.2. Nomenclature of esters

    The nomenclature of esters follows some steps. When naming esters the alkyl

    group R’ is named followed by the name of RCOO- group.

    The group name of the alkyl or aryl portion is written first and is followed by the

    name of the acid portion. In both common and International Union of Pure and

    Applied Chemistry (IUPAC) nomenclature, the -ic ending of the corresponding acid

    is replaced by the suffix –ate. Some examples of names of esters are given in Table

    8.1.


    8.1.3. Physical properties and uses of Esters


    B. Comparing boiling points of alcohols, carboxylic acids and esters

    Materials and Chemicals

    Propan-1-ol, propanoic acid and methyl ethanoate, test tubes, test tube holders

    (lacks), heaters, and thermometers.

    Procedure

    1. Put 10 mL of each substance in a labeled test tube.

    2. Boil carefully substances are volatile and flammable

    3. Use a thermometer to measure the boiling point of each substance.

    4. Record the results and compare them. Suggest a reason for the difference

    in boiling points of the three substances.

    Conclusion: Esters have lower boiling points than alcohols and carboxylic

    acids because they lack hydrogen bonds. A compound having hydrogen bonds

    has a high boiling point because, to break that bond requires higher energy. 

    Other physical properties of esters

    i. Lower esters have sweet fruity smells

    ii. Melting and boiling points of esters increase as the molecular mass

    increases.

    iii. Small esters are fairly soluble in water but the solubility decreases as the

    length of the chain increases

    8.1.4. Uses of Esters

    Esters find various uses:

    i. They are used as organic solvent

    ii. Due to their aroma, they are used as constituent of fragrance, essential oils,

    food flavoring and cosmetics.

    iii. They are used to manufacture soaps, detergents and glycerol.

    iv. They are used to provide energy in the body

    v. Polyesters are used to produce plastics etc.


    8.2. Preparation and chemical properties of esters


    8.2.1. Preparation of Esters

    The preparation of esters involves different types of reaction such as esterification,

    reaction of an acid chloride with an alcohol and the reaction of acid anhydrides

    with alcohols.

    1.Esterification reaction

    In units five and seven, it is mentioned that esters can be produced by a reaction

    between alcohols and carboxylic acids in strong acidic medium acting as a catalyst.

    The acid is commonly a concentrated sulphuric acid, under reflux (Figure 8.3). The

    reaction is generally called “Esterification” (a condensation reaction which involves

    the addition of the alcohol and acid molecules followed by an elimination of a

    water molecule).