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    Lesson 14 Acidic and Basic Character of Organic Compounds

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    This article deals with the acidic and basic nature of organic compounds. the types of compounds are alcohols, carboxylic acids and amides

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    Lesson 14 Acidic and Basic Character of Organic Compounds

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    dela2
    543 views35 pages
    This article deals with the acidic and basic nature of organic compounds. the types of compounds are alcohols, carboxylic acids and amides

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    © © All Rights Reserved

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    PPTX, PDF, TXT or read online from Scribd

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    This article deals with the acidic and basic nature of organic compounds. the types of compounds are alcohols, carboxylic acids and amides

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    543 views35 pages

    Lesson 14 Acidic and Basic Character of Organic Compounds

    Uploaded by

    dela2
    This article deals with the acidic and basic nature of organic compounds. the types of compounds are alcohols, carboxylic acids and amides

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    of 35

    Lesson 14

    ACIDIC AND BASIC CHARACTER


    OF
    ORGANIC COMPOUNDS

    Acidity Measurements
    The acidity constant, Ka, measures the extent to which a Brnsted acid
    transfers a proton to water
    [A] [H3O+]
    Ka = and pKa = log Ka
    [HA]
    Relative acidities are more conveniently presented on a logarithmic scale,
    pKa,

    pKa Values for Typical OH Compounds

    ACIDITY OF ALCOHOLS, PHENOL AND CARBOXYLIC ACIDS


    Brnsted-Lowry definition of acid
    An acid is a proton donor
    Note: a proton is a hydrogen ion (H+)
    An acid in solution sets up this equilibrium:

    hydroxonium ion

    STRENGTHS OF WEAK ACIDS

    The strengths of weak acids are measured on the pKa scale. The smaller the
    number on this scale, the stronger the acid is.

    Ethanoic
    acid

    4.76

    Phenol

    10.00

    ethanol

    Increasing
    Acidity

    about 16

    Ethanol is so weak with a pKa of about 16 that it hardly counts as


    5
    acidic at all!

    Resonance stabilization accounts for why carboxylic acids are more acidic
    than other compounds with OH bondsnamely alcohols and phenols.

    To understand the relative acidity of ethanol, phenol and acetic acid, we


    must compare the stability of their conjugate bases and use the following
    rule:
    - Anything that stabilizes a conjugate base A: makes the starting acid HA more
    acidic.

    ACIDITY OF ETHANOIC ACID


    The ethanoic acid molecule has a hydroxyl group attached to the carbonyl group. The
    negative charge on the ethanoate ion is delocalized with the C=O double bond. Carboxylic
    acids are therefore more acidic than phenol.

    The dotted line represents the delocalisation. The negative charge is written
    centrally on that end of the molecule to show that it isn't localised on one of
    the oxygen atoms.
    The more you can spread charge around, the more stable an ion becomes. In
    this case, if you delocalise the negative charge over several atoms, it is going
    to be much less attractive to hydrogen ions - and so you are less likely to reform the ethanoic acid.
    7

    ACIDITY OF ETHANOL
    Ethoxide, the conjugate base of ethanol, bears a negative charge on the O
    atom, but there are no additional factors to further stabilize the anion.
    Because ethoxide is less stable than acetate, ethanol is a weaker acid than
    acetic acid.

    ACIDITY OF PHENOL
    Phenoxide, the conjugate base of phenol, is more stable than ethoxide, but less stable
    than acetate because acetate has two electronegative O atoms upon which to delocalize
    the negative charge, whereas phenoxide has only one.

    Phenoxide ion
    Phenols (pKa ~10) are much more acidic than alcohols (pKa ~ 16) due to resonance
    stabilization of the phenoxide ion
    Phenols react with NaOH solutions (but alcohols do not), forming salts that are soluble in
    dilute aqueous solution

    Inductive Effect :
    Inductive effect is defined as permanent displacement
    of shared electron pair in a carbon chain towards more
    electronegative atom or group.

    10

    Types of Inductive effect :


    1.Negative Inductive Effect :
    (I effect, Electron withdrawing effect)
    when an electronegative atom or group(more electronegative than
    hydrogen) is attached to the terminal of the carbon chain in a
    compound, the electrons are displaced in the direction of the attached
    atom or group.
    -NO2 > -CN > -COOH > F > Cl > Br > I > OH > C6H5> H

    11

    2. Positive Inductive effect :


    (+I effect, Electron releasing effect)
    When an electropositive atom or group (more electropositive
    than hydrogen) is attached to the terminal of the carbon chain
    in a compound, the electrons are displaced away from the
    attached atom or group.
    (CH3)3C- > (CH3)2CH- > -C2H5 > - CH3.

    12

    Inductive effect is useful in explaining the strength of some organic acids and bases.
    a) Effect of substituent on the acid strength of aliphatic acids.
    HCOOH > CH3COOH > (CH3)2CHCOOH
    Reason : Acidic strength decreases as +I effect of the alkyl group increases.
    b) O2NCH2COOH > FCH2COOH >CICH2COOH >BrCH2COOH> ICH2COOH > CH3COOH
    Reason : Acidic strength decreases as -I effect of the group or halogen decreases.

    13

    14

    INDUCTIVE EFFECTS
    Electronegative atoms can draw negative charge toward themselves,
    which can lead to considerable stabilization of conjugate bases.
    Electron-withdrawing groups make an alcohol a stronger acid by
    stabilizing the conjugate base (alkoxide)

    15

    THE INDUCTIVE EFFECT IN ALIPHATIC CARBOXYLIC ACIDS

    Acidity increases
    - Due to stabilizing effect of EWGs on the conjugate base (the carboxylate ion)

    17

    18

    Basic character of aliphatic amines, amides and aromatic amines

    pKb
    15

    amides

    Phenylamine(aniline)
    (an aromatic amine)

    C6H5NH2

    9.4

    ammonia

    NH3

    4.8

    methylamine

    CH3NH2

    3.4

    ethylamine

    CH3CH2NH2

    3.2

    Aliphatic
    amines

    Kb = base dissociation constant


    pKb =-log10Kb

    Basicity
    increases

    Basicity of Aliphatic amines


    For aliphatic amines, base strength increases with the size and number of alkyl
    groups attached to the nitrogen atom.
    Alkyl groups donate electron density toward the nitrogen atom, increasing the
    ability of the N atom to donate its lone pair of electrons.
    (an example of a positive inductive effect)

    R = alkyl group

    21

    BASICITY OF AROMATIC AMINES

    Aromatic amines(e.g. phenylamine, pKb 9.4 ) are much weaker bases than
    ammonia. The reason for the difference is that the nitrogens lone pair is
    delocalized with the delocalized electrons in the benzene ring and so is
    substantially more difficult to protonate.

    Lone
    pair

    delocalised
    electrons

    Can only be protonated by strong acids

    23

    BASICITY OF AMIDES

    Amides are extremely weak acids and also very weak bases much weaker
    bases than amines.
    Amides are regarded as being essentially neutral in water, eg. Ethanamide
    (CH3CONH2) has a pH of 7.

    24

    Amides are NOT basic because the nitrogen lone pair is no longer
    available for protonation. Instead it is delocalized with the carbonyl group.

    Recall: a base is an electron pair donor

    lone pair

    Note: protonation refers to the addition of H+

    delocalised
    lone pair

    Amino acids contain 2 functional groups

    They all have a similar structure - the identity of R1 and R2 vary

    ZWITTERIONS
    a zwitterion is a dipolar ion
    it has a plus and a minus charge in its structure
    a proton from the COOH group moves to NH2
    amino acids exist as zwitterions at a certain pH
    the pH value is called the isoelectric point
    produces increased inter-molecular forces
    melting and boiling points are higher
    A zwitterion is a compound with no
    overall electrical charge, but which
    contains separate parts which are
    positively and negatively charged.

    Acid/base properties of Amino acids


    amino acids possess acidic and basic properties due to their
    functional groups
    they will form salts when treated with acids or alkalis.

    28

    30

    32

    PROTEINS

    Neutral amino acids


    If the R group does not contain any acidic groups, the amino acid is neutral overall

    Acidic amino acids


    If the R group has more acidic groups then the amino acid is acidic.

    Basic amino acids


    If the R group has more basic groups then the amino acid
    is basic.

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