ACID BASE

PRAMUDJI HASTUTI
BIOCHEMISTRY DEPARTMENT
FACULTY OF MEDICINE
1
Is it different when :

Drug swallow with water

Drug swallow with soft drink
Drug swallow with syrup (acid)

- Why the pH must be

controlled/how?

2
Acid : litmus paper red
Base : litmus paper blue

ARRHENIUS THEORY :
+
Acid : substances in the water yield H ion
_
Base : substances in the water yield OH ion

BRNSTED-LOWRY THEORY:
+
Acid : substances yield proton (H ) / donor
proton

Base : substances combines with proton /

acceptor proton 3
LEWIS THEORY

Acid : substances accept electron pairs

(has empty orbital)
Base : substances give electron pairs
(has free electron pairs)

H+ + :O:H H:O:H

H H
H+ + : N:H H:N:H H+ + NH3 NH4+
H H
coordination 4
 _
HCl H + Cl
+
H2SO4 H+ +
_
HSO4

_ _
HCN H + CN
+
HSO4 H+ +
=
SO4

_ +
CH3COOH H + CH3COO NH4 H+ +
+

_
NH3

_
H2CO3 H + HCO3
+
NH3 H+ +
_
NH2
5

_ _
 Weakest acid strongest conjugate base
_
(HCN) CN combines firmly with proton

Strongest acid weakest conjugate base

_
(HCl) Cl combines loosely with proton

Substances : act both as acid & base =

amphoteric/ amphiprotic
_
HOH H + OH
+
(acid)
HOH + H+ H3O+ (base)
_
NH3 H + NH2
+
(acid)
NH3 + H+ NH4+ (base) 6
 1) HCl + HOH H3O+ + Cl-
_
2) CH3COOH + HOH H3O + CH3COO +

_
3) CH3COOH + NH3 NH4 + CH3COO +

+
1) most H + H2O H3O very strong acid
+

(reaction tend to the right)

_
2) most H + CH3COO CH3COOH
+

Relatively few with water weak acid in

water
(reaction tend to the left)
_
3) in ionization : CH3COO & NH4+ (acid >>>)

CH3COOH is strong acid 7

ACID STRENGTH DEPENDS ON MOLECULAR
STRUCTURE
pKa
Acetic acid 4.75 (CH3COOH)
Monochloroacetic 2.85 (CH2ClCOOH)
Dichloroacetic 1.48 (CHCl2COOH)
Trichloroacetic 0.70 (CCl3COOH)

electronegative Cl >>> H
attract electrons >>
proton release >>
lower pK pH <<

K = - log K = pK ~ express their tendency to ionized

8
K & pK carboxylic acids
Acid K pK
Acetic 1.76 x 10-5 4.75
Glutaric (1) 4.58 x 10 -5 4.34
(2) 3.89 x 10 6 5.41
Citric (1) 8.40 x 10 -4 3.08
(2) 1.80 x 10 -5 5.74
(3) 4.00 x 10 -6 5.40

dual role weak acids & weak bases

example : active site of enzyme :
- proton donor (acid) in one catalytic cycle
- in other stage can bind proton (base)
9
MONOPROTIC & POLYPROTIC ACID
- Monoprotic pK
HCl 1
Formic acid (HCOOH) 3.75
Acetic acid (CH3COOH) 4.76
Lactic acid 3.86
Ammonium ion 10.25

Diprotic
Carbonic acid 6.37 , 10.25
Succinic acid 4.21 , 5.64
Glutaric acid 4.34 , 5.41

Triprotic acid

Phosphoric acis 2.15 , 6.82 , 12.38

Citric acid 3.08 , 4.74 , 5.40
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SALT HYDROLYSIS

1 Kation/anion : weak acid/base neutral

Li+, Na+, K+, Ba++, Sr++ /Cl-, NO3-, SO4=

2. Kation/anion : strong acid/base neutral

CHCOONH4

3. Kation : strong acid (weak base) & anion :

weak base (strong acid) acid solution
NH4Cl, NH4NO3, (NH4) 2SO4

4. Kation : weak acid (strong base) & anion :

strong bas (weak acid) base solution 11

CHCOO3Na, NaCN, NaF, Na2CO3

DISSOCIATION WATER,
HYDROGEN ION CONCENTRATION & pH
_
HOH H + OH +

_
Acid : H > OH
+
_
Base : OH > H+
_
pH of 1 N H = 0
+
pH of 1 N OH = 14
pH scale : 0 - 14

pH body fluid : normally : slight variation

pH blood serum : 7,35 7,45
7 acidotic coma
7,8 tetany

variation tissue pH variation blood pH & vice versa 12

material pH Material pH

Blood serum 7.35-7.45 Urine 4.8-7.5

Cerebrospinal fluid 7.35-7.45 Feces 7.0-7.5
Aqueous humor of eye 7.4 Tears 7.4

Saliva 6.35-6.85 Milk 6.6-6.9

Pure gastric juice 0.9 Skin 6.2- 7.5
Pancreatic juice 7.5-8.0 Kupffer cell Liver 6.4-6.5
Intestinal juice 7.0-8.0 Peripheral cell liver 7.1-7.4

Hepatic duct bile 7.4-8.5 Central cell liver 6.7-6.9

Gall bladder bile 5.4-6.9

_
Except gastric juice : concentration H & OH very small
+

pH serum = 7,4 H+ = 0.0000000394;

pH 7,3 H+ = 0.0000000500
25% H+ in pH 7,3 more than in pH 7,4 13
DISSOCIATION WEAK ACID
_
HA H + A
+
_
H +A
+

dissociation constant (K) =

H+
_
Acetic acid K = 1.86 X 10 5 = 0.0000186
_
HCN K = 7.2 X 10 10 = 0.00000000072
K Acetic acid : thousand times greater than
HCN
_ _
H3PO4 H + H2PO
+
4 K1 = 1.1 x 10 2

_ = _
H2PO4 H+ + HPO 4 K2 = 2 X 10 7
= _3 _
HPO H + PO
14
+
K = 3.6 X 10 12
EFFECT SALT IN DISSOCIATION ACID & BASE,
BUFFER SOLUTION

- Salt weak acid in weak acid sol

- dissociation weak acid
- less acidity & higher pH than when salt absent
_ _
CH3COOH CH3COO + H+ CH3COOH< CH3COO

_ _
CH3COONa CH3COO + Na+ CH3COOH= CH3COO

Equilibrium reaction shifed to the left (increasing

_
CH3COO ) H+ ions pH

pH weak acid solution & its salt : determined by ratio

salt/ acid
15
weak hydroxides & their salt (NH4OH & NH4Cl)

_
NH4Cl NH4 + Cl
+
NH4Cl = H4 +
_
NH4OH NH 4
+
+ OH NH4OH>>NH4 +

_
NH4Cl increase OH pH

- Weak acid & their salt

- weak base & their salt buffer sol

-Have capacity to resisting changes of pH when

acid/alkalines are added to them 16

99 ml water (pH 7) + 1 ml 0.1 N HCl
H+ = 0,001 N pH = 3

99 ml buffer solution (0,1 N acetic acid & 0,1 M sod

acetate pH = 4.73)
+ 1 ml HCl pH = 4.72

99 ml water + 1 ml 0.1 N NaOH pH = 11

99 ml buffer solution (0,1 N acetic acid & 0,1 M sod

acetate pH = 4.73)
+ 1 ml HCl pH = 4.74
17
HENDERSON-HASSELBALCH EQUATION for buffer sol.
[salt]
pH = pKa + log
[acid]
[conjugate base]
pH = pKa + log
[acid]

[proton acceptor]
pH = pKa + log
[proton donor]

BUFFER pH & CAPACITY

pH determine by
1) pKa smaller pH << / pKa higher pH >>
2) Ratio salt/acid , [salt] >> [acid] pH >> 18
BUFFER CAPACITY :

determined by pH change caused by addition strong

acid / alkali determine by ratio salt/acid

a) 10 ml 0,1 M CH3COONa pH = 4,73

10 ml 0,1 N CH3COOH

+ 1 ml 0,1 N HCl
( HCl convert 1 ml 0.1 M salt acid)

pH = 4.73 + log 9/11 = 4.64

pH change = 4.73 - 4.64 = 0.09
19
b) 10 ml 0,025 M CH3COONa pH = 4,73
10 ml 0,025 N CH3COOH

+ 1 ml 0,1 N HCl
( HCl convert 4 ml 0.025 M salt acid)

pH = 4.73 + log 6/14 = 4.36

pH change = 0.37

20
c) 16 ml 0,1 M CH3COONa
4 ml 0,1 N CH3COOH
pH = 4.73 + log 16/4 = 5.33

+ 1 ml 0,1 N HCl
( HCl will convert 1 ml 0.1 M salt acid)

pH = 4.73 + log 15/5 = 5.207

pH change = 5.33 5.207 = 0.123

21
Maximum efficiency :
- ratio salt & acid = same

IMPORTANT of BUFFER
- regulating pH fluids, tissues
- Laboratory : control pH
- media culture,
- reactions that catalyzed by
enzymes

22
BUFFERS OF BLOOD PLASMA :

- Carbonate/bicarbonate (greatest conc.)

0.025 M HCO3 & 0.00125 M H2CO3 (20/1)
pH = 6.1 + log 20/1 = 7.4

- phosphate/biphosphate

- protein/proteinate
23
BUFFERS OF RED BLOOD CELLS :
- Protein Hb >>>(pH = 7.25)
(carbonate/bicarbonate <<)

BUFFERS TISSUE FLUIDS & TISSUES:

smaller protein

Some Acid continually formed in tissue cells :

sulfuric, phosphoric, lactic, acetocatic acid,
-hydroxybutiric acid etc

24