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LECTURE 7

Brnsted-Lowry acids & bases


Conjugate acid-base pairs
Strength of acids & bases
Constant of acidity/basicity
pH (revisited)
pH of salts
Lewis acids & bases
By the end of this lecture you should

Understand the concepts of acids & base


Understand the concepts of
acid-base conjugate pairs
Quantify the strength of acids & bases
Be able to calculate the ionic
equilibrium in solutions of acids & bases
Understand the concept of pH &
calculate the pH of salts

http://teacherweb.com/CA/NovatoCharterSchool/Betz6thGrade/gallery1.aspx

Reading for this lecture

Chapters
14.1-14.2
14.5-14.9
14.11

Pages
526-531
536-553
557-560

Chapters
17.1-17.2
17.5-17.9
17.11

Pages
656-661
668-689
694-696

Three theories of acids and bases


Lewis
Lewis acid is an electron pair acceptor
Lewis base is an electron pair donor

Brnsted-Lowry
Acid is a proton donor
Base is a proton acceptor

Arrhenius
Acid produces H+(aq)
Base produces OH-(aq)

Brnsted-Lowry:
Based on proton-transfer reactions

H 2 SO4 H 2O HSO4 H 3O
acid

base

base

HSO4 H 2O

SO42 H 3O

H 2 SO4
H 3O +
!! Acid is a substance that donates a
proton
Base is a substance that accepts a
proton

HSO4H 2O
SO42-

acid

Mono and poly protic acid


Monoprotic acid has only one proton that is able to be donated
Polyprotic acid has more than one proton that are able to be donated
H 3 PO4 H H 2 PO4

H 2 SO4

H 2 PO4 H HPO42
HPO42 H PO43

oxalic acid

H 3 PO4 3H PO43

citric acid
Amphoterism
A substance that is able to donate and accept a proton is amphoteric
H 2O, HSO4 , H 2 PO4 , HPO42 , HCO3 , ...

Conjugate acid-base pairs


All Brnsted-Lowry acid-base reactions
involve
the transfer of a proton
two conjugate acid-base pairs
conjugate pair 2

CH 3COOH H 2O CH 3COO H 3O
conjugate pair 1
conjugate pair 2

!!
The position of equilibrium
favours transfer of the
proton to the stronger bas

CH 3CH 2 NH 2 H 2O CH 3CH 2 NH 3 OH
conjugate pair 1

Relative strengths of acids and bases

The stronger the acid


the weaker the conjugate base
And vice versa
strong acids
HCl , HBr , HI , HNO3 , HClO3 , HClO4
H 2 SO4
strong bases
LiOH , NaOH , KOH , RbOH , CsOH
Mg (OH ) 2 , Ca (OH ) 2 , Sr (OH ) 2
all completely dissociated

Acid dissociation
(always written as the donation of a proton in forward reaction)

HA H 2O A H 3O

A H 3O

Kd Ka
HA

The same reaction (acid deprotonation) can be written also as

HA OH

A H 2O HA OH

HA H 2O A H 3O

Kb

A H 2O HA OH

A H 3O

Ka
HA
Kb

HA OH

H 2O H 2O H 3O OH

K K a K b K w

K a , HA

Kw

K b , A

For acids
The acid-dissociation constant Ka
(also called as a constant of acidity
is the same as the dissociation
constant Kd of that acid

Base dissociation

(always written as the acceptance of a proton in forward reaction)

B H 2O BH OH

BH OH

K d Kb
B

The same reaction (base protonation) can be written also as

B H 3O

BH H 2O B H 3O

B H 2O BH OH

Ka

BH

BH OH

Kb
B

B H 3O

BH H 2O B H 3O

Ka

H 2O H 2O H 3O OH

K K b K a K w

BH

Kb,B

Kw

K a , BH

For bases
The base-dissociation constant Kb
(also called as a constant of basicity
is the same as the dissociation
constant Kd of that base

The strengths of acids and bases


For acids :
strength expressed as the dissociation constant
i.e., the constant of acidity
Ka Kd

pK a log K a

For bases:
Strength expressed as the dissociation constant
i.e., as the constant of basicity
Or as a weakness of conjugate acid,
Kb K d
pKb log K b 14 pK a ,conj
K a ,conj

Kw
Kb

for conjugate pairs


K a Kb K w

K a ,stronger K a ,weaker
pK a pK b 14

pK a ,stronger pK a ,weaker

Fractional dissociation degree of dissociation

!!

cdissociated

cbulk

Represents the percentage of molecules dissociated into ions


Depends on the strength of the acid/base (pKa /pKb) and on the
concentration
Ranges from 0 to 1 (or 0 to 100%)

cdissociated cbulk cundissociated

cbulk
cbulk

cundissociated
cbulk

-1.E-04

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
7.E-20

1.E-04
c

2.E-04

3.E-04

Equilibria calculations
Weak acid dissociation

HA A H

1. The simplest method (high concentration of the acid)


H A
Ka
HA

The dissociation of water


has been neglected

A
{EN } H

cHA HA A

simplification

{SB}

cHA

H
Ka
cHA

HA cHA

H K a cHA

HA H A
A

cHA

H 2O H OH

H H

Equilibria calculations
Weak acid dissociation HA A H
2. The simple method (low concentration of the acid)
H A
Ka
HA
A
{EN } H

cHA HA A

{SB}

HA cHA


A cHA H


K a H

K
H a
2

HA H A
H 2O H OH

H
Ka
cHA H
H

The dissociation of water


has been neglected

H H
K a cHA 0
4cHA
1

Ka

Equilibria calculations
Weak acid dissociation HA A H
3. The rigorous method (all concentrations of the acid)
H A
Ka
HA
A OH

{EN } H
{SB} cHA HA A

K w H OH

Ka

Kw
Kw
cHA H
H
3


K a H

K a cHA K w H

H solved numerically

K
w K a

(22/3 3 9cK a 2

9cK

2
a

2 K a 3 18 K a K w 4 3cK a K a 2 3K w 2 K a 3 18K a K w
2

2 3 2 3cK a K a2 3K w

9cK a
2

9cK

2
a

2 K a 18 K a K w 4 3cK a K a 3K w 2 K a 18 K a K w
3

2Ka ) / 6

Acetic acid dissociation


Calculation methods comparison
1.E-03

1.E-04

1.E-05

[H+]
1.E-06

Metho
d 1
Metho
d 2

1.E-07

1.E-08

1.E-09

1.E-07

1.E-05

cHA

1.E-03

1.E-01

Dissociation of a weak acid the pKa effect


1.E+00

pKa=0
pKa=1

1.E-01

pKa=2
pKa=3

1.E-02

pKa=4
pKa=5

1.E-03

pKa=6
pKa=7

[H+]

1.E-04

pKa=8
pKa=9
pKa=10

1.E-05
1.E-06
1.E-07
1.E-08
1.E-09

1.E-07

1.E-05

1.E-03

cHA

1.E-01

1.E+01

% dissociation of a weak acid the pKa effect


100

pKa=0
pKa=1

10

pKa=2
pKa=3

% of dissociation
1

pKa=4
pKa=5
pKa=6

0.1

pKa=7
pKa=8

0.01

pKa=9
pKa=10

0
1.E-08 1.E-07 1.E-06 1.E-05 1.E-04 1.E-03 1.E-02 1.E-01 1.E+00

cHA

Equilibria calculations
Weak base dissociation

B H 2O BH OH

The dissociation of water


The simple method (low concentration of the acid) has been neglected
BH OH

Kb
B

B H 2O BH OH

OH

{EN } BH

cB B BH

{SB}

B cB


BH cB OH

H 2O H OH

OH OH

OH
Kb
cB OH
OH


Kb OH

K
OH b
2

K b cB 0

4cB
1
K b

The formulae for bases


are the same as for acids
when you replace
[H+] [OH-]
Ka Kb

Equilibria calculations

pH of salts

Salt is a product of reaction between an acid and a base

Rule of thumb:

K a Kb

pH 7

K a Kb

pH 7

A salt of a strong acid and a strong base will be neutral (pH = 7)

NaOH HCl NaCl H 2O

A salt of a weak
A salt of a strong acid and a weak base will be acidic (pH < 7)acid
and a weak
NH 4OH HCl NH 4Cl H 2O
base :
(NH4CN)
A salt of a weak acid and a strong base will be basic (pH > 7)
Depends on
NaOH HCN NaCN H 2O
mutual
size of Ka & Kb

Equilibria calculations

pH of salts

A salt of a weak acid and a strong base will be basic (pH > 7)

NaOH CH 3COOH CH 3COONa H 2O

Dissociation and hydrolysis


CH 3COONa CH 3COO Na

(fully dissociated)

CH 3COO H 2O CH 3COOH OH

(hydrolysis)

Equilibria calculations

pH of salts

A salt of a weak acid and a strong base will be basic (pH > 7)

NaOH CH 3COOH CH 3COONa H 2O

Dissociation and hydrolysis


CH 3COONa CH 3COO Na

(fully dissociated)

CH 3COO H 2O CH 3COOH OH

(hydrolysis)

5 equations to solve
{SB1}

Na cCH3COONa

{SB 2}

CH 3COOH CH 3COO

{EN }

H Na
CH 3COO
OH

CH 3COO H

Ka Kd
CH 3COOH

K w H OH

cCH3COONa

Quite messy
calculation

Salt of a weak acid and a strong base -- hydrolysis


H


c K a H

K w H

K a Kw

2.E-07
pKa=0

2.E-08

pKa=1
pKa=2

2.E-09

pKa=3
pKa=4

[H+]

pKa=5

2.E-10

pKa=6
pKa=7

2.E-11

pKa=8
pKa=9

2.E-12
1.E-09

pKa=10

1.E-07

1.E-05

1.E-03

csalt

1.E-01

1.E+01

Salt of a weak acid and a strong base -- hydrolysis


H

c K a H

K a K w

c Ka


K w H

K a K w
c

K a K w 0

pH

1
14 pK a log c
2

2.E-07

2.E-07

2.E-08

2.E-08
2.E-09

2.E-09

[H+]

[H+]

2.E-10

2.E-10
2.E-11
2.E-12

2.E-11

1.E-10 1.E-08 1.E-06 1.E-04 1.E-02 1.E+00


csalt

2.E-12
1.E-10 1.E-09 1.E-08 1.E-07 1.E-06 1.E-05 1.E-04 1.E-03 1.E-02 1.E-01 1.E+00
csalt

Salt of a strong acid and a weak base -- hydrolysis


OH

c K b OH

OH

K b K w

c Kb


K w OH

K b K w
c

K b K w 0

pOH

1
14 pKb log c
2

2.E-07

2.E-07

2.E-08

2.E-08
2.E-09

2.E-09

[OH-]

[OH-]
2.E-10
2.E-10
2.E-11
2.E-12

2.E-11

1.E-10 1.E-08 1.E-06 1.E-04 1.E-02 1.E+00


csalt

2.E-12
1.E-10 1.E-09 1.E-08 1.E-07 1.E-06 1.E-05 1.E-04 1.E-03 1.E-02 1.E-01 1.E+00
csalt

Salt of a weak acid and a weak base


NH 4CN NH 4 CN

(fully dissociated)

NH 4 H 2O NH 3 H 3O
CN H 2O HCN OH
2 H 2O H 3O OH
six unknowns

K a , NH 4

K b ,CN

Kw

NH 4 NH 3 csalt c
{SB 2} CN HCN csalt c

Ka

Kw

K a , HCN

NH 4 , CN , NH 3 , HCN , H 3O , OH

{SB1}

{EN }

Kw

K b , NH3

NH 4 H
CN
OH
H CN

HCN

NH 4 OH

Kb
NH 3

K w H OH

K a x K w

x H

K b x K w

K b x 3 K a K w x

x2

Salt of a weak acid and a weak base

pH f c, K a , K b
csalt=10-5 mol/L

csalt=10-4 mol/L

csalt=10-3 mol/L

pH=4

pH=5

pH=3

pH=10

pH=9

pH=11

11

11

11

Salt of a weak acid and a weak base - pH


7.0
6.5

pKa=3,
pKb=4

6.0

pKa=3,
pKb=5

5.5

pKa=3,
pKb=6

pH 5.0

pKa=3,
pKb=7

4.5

pKa=3,
pKb=8

4.0

pKa=3,
pKb=9

3.5

pKa=3,
pKb=10

3.0

-8

-7

-6

-5

-4

-3

-2

-1

-log(csalt)

See the Excel sheet

Salt of a weak acid and a weak base - pH


7.0
6.5

pKa=3,
pKb=4

6.0

pKa=3,
pKb=5

5.5

pKa=3,
pKb=6

pH 5.0

pKa=3,
pKb=7

4.5

pKa=3,
pKb=8

4.0

pKa=3,
pKb=9

3.5

pKa=3,
pKb=10

3.0

-8

-7

-6

-5

-4

-3

-log(csalt)

-2

-1

Salt of a weak acid and a weak base pH at high concentrations


c

K a x K w

K b x K w

x2

K b x3 K a K w x

x H

K a K w
Kb

Concentration will get higher


if this expression gets lower

K b x 3 K a K w x 0
K b x 3 K a K w x

1
log H log K a log K w log K b
2
pH =

1
pK w + pK a - pK b
2

pH 7

pK a pK b
2

K b x 2 K a K w
x2

K a K w
Kb

pH of acids, bases and salts overview

pH log H
ACID

OH

pOH log

pH 14 pOH

None

Weak

Strong

H2 O

HCN

HCl

H K w

H K a c

H c

NH4OH

NH4CN

NH4Cl

OH K b c

K
H K w a
K

NaOH

NaCN

BASE

None

Weak

Strong

OH c

K a K w
c Ka

OH

K b K w
c Kb

NaCl
H K w

. the bulk concentration (what has been put into the water) of acid/base/salt

pH of acids, bases and salts example


pK a 9.2
ACID

pK b 4.8

c 0.25 mol/L

None

Weak

Strong

H2 O

HCN

HCl

pH 7

pH 4.9

pH 0.6

NH4OH

NH4CN

NH4Cl

pH 11.3

pH 9.2

pH 4.9

NaOH

NaCN

NaCl

pH 13.4

pH 11.3

pH 7

BASE

None

Weak

Strong

. the bulk concentration (what has been put into the water) of acid/base/salt

pH of acids, bases and salts HOMEWORK ammonium


formate
pK a 3.8
pK b 4.8
c 0.158 mol/L
ACID

None

Weak

Strong

BASE

HBr
None

NH4OOCH
Weak

KOH
Strong

. the bulk concentration (what has been put into the water) of acid/base/salt

Lewis Acids and Bases


A Brnsted-Lowry base must have an unshared (free) pair of
electrons
for binding the proton.

H :N H H
|

N H
|

NH

Lewis base is an electron-pair donor


(provider)
Lewis acid is an electron-pair acceptor (user)
Lewis acids & bases = All Brnsted-Lowry acids & bases + some
H
H
H
H
other
|

H B :N H H B N H

involved

No protons

Lewis Acids and Bases


A Brnsted-Lowry base must have an unshared (free) pair of
electrons
for binding the proton.

H :N H H
|

N H
|

NH

Lewis base is an electron-pair donor


(provider)
Lewis acid is an electron-pair acceptor (user)
Lewis acids & bases = All Brnsted-Lowry acids & bases + some
H
H
H
H
other
|

H B :N H H B N H

involved

No protons

Lewis Acids and Bases


mechanism