ACIDS, BASES, pH AND pKA

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 After studying this topic, you should be able to…

• Define Brønsted-Lowry acids and bases as proton donors and

acceptors; and distinguish between acid strength and acid
concentration
• Predict the conjugate form of typical biochemical groups given
a pKa value and a pH
• Perform calculations involving pH, Ka, pKa , Kw and pOH, such as
calculating the pH of dilute solutions of strong acids and bases

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 A Brønsted-Lowry acid, HA, is a proton donor
• Acid dissociation half-reaction:
HA ⇌ H+ + A−
Acetic acid Acetate ion
O O

H3C C H3C C

O H O H

Acid Conjugate base

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A Brønsted-Lowry base, B, is a proton acceptor
• Base protonation half-reaction:
B + H+ ⇌ BH+
Ammonia Ammonium ion

H H

N N
H H H H
H H

Base Conjugate acid

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An acid/base reaction is the movement of a proton from
an acid to a base; it is the sum of two half-reactions
H3C–COOH ⇌ H3C–COO− + H+
H+ + NH3 ⇌ NH4+
--------------------------------------------------------------------------

H3C–COOH + NH3 ⇌ H3C–COO− + NH4+

• More generally, the full reaction can be written

HA + B ⇌ A− + BH+
• …but the mirror image is just as valid!
A− + BH+ ⇌ HA + B

• Two conjugate acid/base pairs in every acid/base reaction

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 Acid and base are relative terms
• Water acts as both a • H2O ⇌ OH− + H+
base and an acid • H2O + H+ ⇌ H3O+
[added together…]
• H2O + H2O ⇌ H3O+ + OH−

• As can other weak acids

• CH3COOH + H2O⇌ CH3COO− + H3O+
exposed to stronger
acids • CH3COOH + HCl ⇌ CH3C(OH)2+ + Cl−

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0 1 M HCl 1.0
1 Stomach acid 1.5
2 Lemon juice 2.0
Acidic
Acidity of a solution is measured by
its pH, the negative base-10
logarithm of the hydrogen ion

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4 Lysosome 4.0
concentration in molar
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6 Milk 6.5

7 Water 7.0
8
Neutral
Blood 7.4 𝑝𝐻 =− log 10 ¿ ¿
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Basic (alkaline)

10

11

12 Ammonia
13 7
 Species Dissociation pKa
A strong acid Hydrochloric HCl ⇌ Cl− + H+ c. −4
acid
has a low pKa

very weak conjugate

Hydronium H3O+ ⇌ H2O + H+ −1.7
ion

Carboxylic –COOH ⇌ –COO− + H+ 2…5

acids
HA ⇌ H+ + A− Dihydrogen H2PO4− ⇌ HPO42− + H+ 7

bases
phosphate

bases
acids, with
Protonated –NH3+ ⇌ –NH2 + H+ 8 … 11

𝐾 𝑎=¿ ¿ amines

conjugate
Phenols –⌬–OH ⇌ –⌬–O− + H+ 10

Strong
Water H2O ⇌ OH− + H+ 15.2
𝑝𝐾 𝑎=− log 10 𝐾 𝑎

with weak
sconjugate
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Strong acids dissociate completely in water to
form hydronium ions
• pH very easy to calculate for
strong acid
• Complete dissociation
HCl  Cl + H
− + • ∴ 1 M [HCl] ⇒ 1 M [H+]
• pH = −log10(1) = 0

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What is the pH of a 1 mM solution of HCl?

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What is the pH of a 1 mM solution of HCl?
Completely dissociates into 1 M H+ and 1 M Cl–

[H+] = 10−3 M

pH = –log10 [H+/M] = –log10 10−3 = 3

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 Strength ≠ concentration
• 1 M acetic acid is a concentrated • 10 mM hydrochloric acid is a
solution of a weak acid dilute solution of a strong acid
• pH 2.4 • pH 2

Strong, concentrated Strong, dilute

2 M H2SO4 10 mM HCl

Weak, concentrated Weak, dilute

1 M CH3COOH 0.1 mM C6H5OH

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 Polyprotic acids have > 1 dissociable proton, so
form several equilibria
• Glycine is diprotic

O OH O O- O O-
C C C
H C NH3+ H C NH3+ H C NH2
H 2.35 H 9.78 H

• Phosphate is triprotic
OH OH O O
HO OH O OH O OH O O
P P P P

2.2 7.2 12.3

O O O O

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 pKa is a "personal scale of acidity" for a chemical group
Below pH 2.35, Above pH 2.35,
protonated COOH deprotonated COO−
predominates predominates
O OH O -
O O O-
C C C
+ +
H C NH3 H C NH3 H C NH2
H 2.35 H 9.78 H
Below pH 9.78, Above pH 9.78,
protonated NH3+ deprotonated NH2
Glycine
predominates predominates
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
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 pH of a strong base can also be calculated
using the ionic product of water
• Empirically measured
H2O ⇌ OH− + H+ • pKw = 14

¿ • Complete dissociation of
strong base
• ∴ 1 M [NaOH] ⇒ 1 M
𝑝𝐾 𝑤 =𝑝𝐻 +𝑝𝑂𝐻 [OH−]
• pOH = −log10(1) = 0
• pH = 14 − pOH = 14 15
What is the pH of a 1 µM solution of NaOH?

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What is the pH of a 1 µM solution of NaOH?
[OH−] = 10−6 M

pOH = –log10 [OH–/M] = –log10 10−6 = 6

pH =14 – pOH = 14 – 6 = 8

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18
BUFFERING

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 After studying this topic, you should be able to…

• Describe the basis of pH buffering

• Be able to select buffers for particular applications, and justify
the choice in reference to the criteria used by Good
• Use the Henderson-Hasselbalch equation to predict the pH of
buffers

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The experimental neutralisation of an acid by a base (or
vice versa) is called a titration
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• Acetic acid titration
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8 H3C–COOH + OH−
7
⇌
6
5 H3C–COO− + H2O
pH

4
3
2 • Molar equivalents = moles of
1
base added / moles of acid
0
0.0 0.5 1.0 originally put in beaker
Molar equivalents of base

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You titrate 100 mL of a 0.2 M weak triprotic acid with 0.2 M
sodium hydroxide. By the time you have added 200 mL of
base, what form will the acid be in?

A. Mostly the monoanion

B. Half-and-half monoanion and dianion
C. Mostly the dianion
D. Half-and-half dianion and trianion
E. Mostly the trianion

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You titrate 100 mL of a 0.2 M weak triprotic acid with 0.2 M
sodium hydroxide. By the time you have added 200 mL of
base, what form will the acid be in?

• They have the same concentration

• Acid: 0.1 L × 0.2 M = 0.02 mol
• NaOH: 0.2 L × 0.2 M = 0.04 mol
• Molar equivalents: 0.04 / 0.02 = 2
• You’ve neutralised the acid twice over
• Almost pure dianion

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 The pH of a solution can be predicted using the
Henderson-Hasselbalch equation
10 Nearly pure
9 Half-neutralised, CH3COO−
8 50:50 mixture,
7 [CH3COOH] = [CH3COO−]
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pH = pKa
5
pKa ≈ 4.8 [𝐴 ]
−
pH

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3 𝑝𝐻 =𝑝 𝐾 𝑎 +log 10
2 [ 𝐻𝐴 ]
1
Nearly pure 0
CH3COOH 0.0 0.5 1.0

Molar equivalents of base

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Around the pKa, an acid buffers (resists)

ga nc e a
o
pl pH f b t
both increases and decreases in pH

ar g o ck

se
s
sh akin rop ba
a
in rea
m y d hen
10

i
tin d t
9

An

ya
8

7
But hardly any change
6
in pH in this region
5 pKa ≈ 4.8 A lot of base
pH

4 A lot of acid buffering range

Rule of thumb
ar as es of

3
pH

Buffers work ± 1 pH
sh cre ak op

2
de id m dr

unit around the pKa

ac tiny

1
pl e
er
A

(but ± 0.6 is safer)

yh

0
0.0 0.5 1.0

Molar equivalents of base

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 pH buffer solutions can be made from weak acids in two
ways
Henderson-Hasselbalch way Titration way
• Mix weak acid, HA • Take weak acid/base at required
HA ⇌ H + A
+ − molarity
• With salt of acid, NaA • Titrate with NaOH/HCl until you reach
NaA ⇌ Na + A
+ − the desired pH
• e.g. buffer at pH 4.8 • e.g. buffer at pH 7.5
– pKa (acetic acid) = 4.8 – pKa (Tris) = 8.1
– Equal concentrations of acetic acid & – Add HCl to Tris-base until pH = 7.5
OH
sodium acetate NH2

OH

HO 26
Cells are buffered by numerous weak acids and bases
Phosphoric acid is triprotic
• Carbonic acid 14
12 pKa3
H2CO3 ⇌ HCO3− + H+

equivalence point
10

equivalence point
• Hydrogenphosphate 8
pKa2

pH
H2PO4− ⇌ HPO42− + H+ 6
4
2 pKa1
Note that the buffering zones
are at the HALF equivalence 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
points, NOT at the equivalence
Molar equivalents of base
points themselves
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 These additional resources may help you meet the intended
learning outcomes of these topics…
• Classic papers
• Self-test materials on Blackboard – Brønsted, B. N. (1923) Some remarks on the concept of
– End of topic quiz acids and bases. Recueil Des Travaux Chimiques Des Pays-
Bas, 42, 718-728.
– Worksheets – Hasselbalch, K. A. (1917) Die Berechnung der
Wasserstoffzahl des Blutes aus der freien und
gebundenen Kohlensäure desselben, und die
Sauerstoffbindung des Blutes als Funktion der
Wasserstoffzahl. Biochemische Zeitschrift, 78, 112-144.
– Henderson, L. J. (1908) Concerning the relationship
between the strength of acids and their capacity to
preserve neutrality. American Journal of Physiology, 21,
173-179.
– Sörenson, S. P. L. (1909) Enzyme studies II: the
measurement and meaning of hydrogen ion
concentration in enzymatic processes. Biochemische
Zeitschrift, 21, 131-200.

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