CIVL 6023 Environmental Chemistry

Proton Exchange Reactions

(Acid/base equilibrium)

Bronsted Concept of Acid/Base

Acid: Species Capable of Donating a Proton

Base: Species Capable of Accepting a Proton

Acid and Its Conjugate Base

Base2 Acid1 Acid2 Base1 pKa

H2O + HAc = H3O+ + Ac- 4.76

H2O + HOCl = H3O+ + OCl- 7.55

H2O + HCN = H3O+ + CN- 9.23

1
 Free Energy of Proton Transfer

HA = H+ + A-

Ka = [H+][A-]/[HA] at equilibrium

Q = [H+][A-]/[HA] non-equilibrium
conditions

Where Q is the reaction quotient

3

Proton Transfer Reactions

Conjugate GoRXN
pKa
Acid/Base kJ/mole
H3O+/H2O 0 0
HAc/Ac- 27.2 4.76
HOCl/OCl- 43.1 7.55
HCN/CN- 52.7 9.23
NH4+/NH3 52.8 9.25
H2O/OH- 79.9 14.0
GoRXN : Energy required for transfer of one mole H+ from acid to water
4

2
 Free Energy of Proton Transfer
General Free Energy Equation

∆Grxn = ∆G°rxn + 2.3RTlogQ

at equilibrium

∆Grxn = 0 and Q = Ka

And

∆G°rxn = -2.3RTlogKa
Where -2.3RT = 5.71 at 25°C 5

P notation

In environmental chemistry, the magnitude of some

important variables [H+], [L], and [e] can range over a very
wide orders of magnitude
→ not easy to use arithmetic scale
→ Log scale is more practical

Using p notation we have:

pH = -log[H+] pL = -log[L] and pe = -log[e]

Where we now assume activity = concentration for

simplicity
6

3
 MONOPROTIC WEAK ACID/BASE SYSTEM (1)

Reaction: HAc +H2O = H3O+ + Ac-

HAc, CT=10-3M, pKa=4.75

Species (4):
H+(simplified from H3O+),
OH- , HAc, Ac-

In order to solve these

4 unknowns (species),
we need 4 equations !!

MONOPROTIC WEAK ACID/BASE SYSTEM (2)

Mass Action:
KW = [H+] [OH-] (1)

[H+ ][Ac - ]
Ka = (2)
[HAc]
Mass Balance:
CT = [HAc] + [Ac-] (3)
Charge Balance:
[H+] = [Ac-] + [OH-] (4)

4
 MONOPROTIC WEAK ACID/BASE SYSTEM (3)

Chose the hydronium ion (H3O+, or simplified as H+)

as the master variable, and put all other species in
terms of [H+].

Combining equations (2) and (3) gives:

[H+ ]
CT = [ Ac - ] + [ Ac - ]
Ka (5)
then equation (5) can be rewritten as:
C TK a
[ Ac - ] =
K a + [H+ ] (6)
Combining equations (3) and (6), we will have:
CT [H+ ]
[HAc ] =
K a + [H+ ] (7)
9

MONOPROTIC WEAK ACID/BASE SYSTEM (4)

Substituting equations (1) and (6) into equation (4) we get:

C TK a KW
[H+ ] = + +
(8)
K a + [H ] [H+ ]

This is a third order polynomial in [H+], and thus [H+] can be solved.
By (1) and the solution of [H+], [OH-] can also be solved.

Rearranging equation (8) will gives:

[H+ ] K
C = (1 + )([H+ ] - W+ ) (9)
Ka [H ]

Using equation (9), a pH vs. pC diagram can be plotted for a series

of acids, showing the relative strength of each acid/base system.

10

10

5
 MONOPROTIC WEAK ACID/BASE SYSTEM (1)

Reaction: HAc +H2O = H3O+ + Ac-

HAc, CT=10-3M, pKa=4.75

Species (4):
H+(simplified from H3O+),
OH- , HAc, Ac-

Pick [H+] as our Master

Variable. pH = -log[H+]

11

11

Using graphical algebra, we can display the

species(unknowns) concentrations across the pH range of
water.

Plot hydronium line: p[H+] = pH (1)

Plot hydroxyl line: p[OH-] = pKW – pH (2)

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6
 pH
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

p[H+] = pH
0

2 p[OH-] = pKW – pH
3

6
pC

10

11

12
[OH-] [H+]
13

14
MonoProtic Acid (HA)
13
PCT=5*10-2, pKa=4.75

13

GRAPHICAL DISPLAY OF EQUATIONS (1)

Using graphical algebra, we can display the species(unknowns)

concentrations across the pH range of water.

Plot hydronium line: p[H+] = pH (1)

Plot hydroxyl line: p[OH-] = pKW – pH (2)

Plot HAc line:

CT [H+ ]
[HAc ] =
K a + [H+ ] (3)

Plot Ac- line: C TK a

[ Ac - ] =
K a + [H+ ]
(4)

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14

7
 CT [H+ ] C TK a
[HAc ] = [ Ac - ] = GRAPHICAL DISPLAY OF EQUATIONS (2)
K a + [H+ ] K a + [H+ ]

If pH < pKa, [H+] >> Ka:

 log[HAc]  logCT
d p[HAc ]
=0
d pH (slope of [HAc] line is 0 ) (5)
 log[Ac-]  pH – pKa + logCT
d p[Ac- ]
= −1 (slope of [Ac-] line is -1 ) (6)
d pH

If pH > pKa, [H+] << Ka:

 log[HAc]  = -pH + pKa + logCT
d p[HAc]
= +1
d pH (slope of [HAc] line is +1 ) (7)
 log[Ac-]  logCT
d p[ Ac - ]
=0 (slope of [Ac-] line is 0 ) (8)
d pH 15

15

pH
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0

1 [HAc] [Ac-]
2

6
pC

10

11

12
[OH-] [H+]
13

14
MonoProtic Acid (HA)
16
[HAc] = [Ac-] @ pH = pKa CT=5*10-2, pKa=4.75

16

8
 Solving the System Composition
The Charge Balance Equation

The bulk solution does not carry net charges:

Charge balance: H3O+ = Ac- + OH-

17

17

GRAPHICAL DISPLAY OF EQUATIONS (3)

HAc, CT = 510-2M, pKa= 4.75

18

18

9
 Solving the System Composition
The Proton Condition

Accounting for Proton Exchange in the System

Adding fully protonated acid to water

Starting Materials: HAc and H2O

Identify Species Accepting a Proton: H3O+

Identify Species Donating a Proton: Ac-, OH-

Proton Condition: H3O+ = Ac- + OH-

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19

Generalized Monoprotic Systems

All monoprotic systems follow the equations and rules

set forth so far. The positioning of the system plots on
pC-pH diagrams will depend only on the pKa and the CT
of the system.

20

20

10
 pH
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0
HOCl OCl- pKa for HOCl = 7.53
1
2 CT= 10-1
3
CT= 10-3
CT= 10-5
4
5
6
pC

7
8
9
10
11
12
13
14
21
Speciation of HOCl

21

pH
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0
CT=10-3
1
2 pKa for CH3COOH = 4.75
for HOCl = 7.53
3 for HCN = 9.40
4

5
6
pC

7
8
9
10

11
12
13
14
22
MonoProtic Acid (HA)

22

11
 GRAPHICAL DISPLAY OF EQUATIONS (4)

We can define a new entity, distribution

coefficient, I, for each species as:

[HAc ] [H+ ]
0 = CT
=
K a + [H+ ] (9)

[ Ac - ] Ka
1 = CT
=
K a + [H+ ]
(10)

where 1  0 + 1 (11)

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23

GRAPHICAL DISPLAY OF EQUATIONS (5)

Monoprotic weak acid, pKa= 4.75

24

24

12
 Use of Distribution Coefficients

αo = [HAc]/CT

α1 = [Ac-]/CT

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25

26

26

13
 Understanding Graphical Representations

Solving Systems Graphically

27

27

Finding the Proton Condition

For single monoprotic acid/base systems
there are two possible ways of composing
the system starting materials:

1.HAc, H2O

2.NaAc, H2O
However, the plot of the system will be the
same no matter how the system is composed.
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14
 pH
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0
CT=10-3
1
2 pKa for CH3COOH = 4.75

4
5
6
pC

8
9

10
11
12
13

14
29
MonoProtic Acid (HA)

29

Equations for Diprotic Acid/Base Systems

Graphical Representation of Diprotic

Systems

(Note: Slides #30-47 are for appreciation

only and are not examinable.)
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15
 There are many important weak acid/base
systems in natural soil and aquatic systems,
and engineered systems (anaerobic digestors).

Examples:

Mono (acetic and propionic acid) and

poly carboxylic acids (citric, oxalic acids)
polyprotic inorganic acids (orthophosphate,
arsenite, arsenate, selenate, hydrogen
sulfide, carbonic acid, etc).
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31

Polyprotic Acid/Base Systems

• Polyprotic Acids
– H2CO3 closed system
– alpha (distribution coefficient) tables
– graphical solutions to equilibrium
problem
• 1mM H2CO3
• 1mM NaHCO3
• 1mM Na2CO3

32

32

16
 Polyprotic acids: Diprotic acids
H2A e.g. H2SO4, H2CO3
• can donate more than one proton/ has
multiple pKas (-logKa)
• Species: H2A, HA-, A2-, H+, OH-
• Mass Action:
H2A = HA- + H+ Ka1 = [HA-][H+]/[H2A]
HA- = A2- + H+ Ka2 = [A2-][H+]/[HA-]
H2O = OH- + H+ Kw = [OH-][H+]
33

33

Polyprotic acids cont’d, H2A

• Mass Balance: CT = [H2A] + [HA-]+ [A2-]
• Charge Balance:
[H+] = [HA-] + 2[A2-] + [OH-]
Plotting the pC-pH diagram ,  values

[H2A] = CT[H+]2/(Ka1 Ka2 + Ka1[H+] + [H+]2) 1

[HA-] = CTKa1[H+]/(Ka1 Ka2 + Ka1[H+] + [H+]2) 2
[A2-] = CTKa1 Ka2 /(Ka1 Ka2 + Ka1[H+] + [H+]2) 3
derived from substituting mass action
equations into the mass balance 34

34

17
  (distribution coefficients)
tables for diprotic system
o = [H2A]/ CT = [H+]2/(Ka1 Ka2 + Ka1[H+] + [H+]2)

1 = [HA-]/CT = Ka1[H+]/(Ka1 Ka2 + Ka1[H+] + [H+]2)

2 = [A2-]/CT = Ka1 Ka2 /(Ka1 Ka2 + Ka1[H+] + [H+]2)

for a given pH, the  values are calculated

and allow quick evaluation of distribution.
Example: Given [HCO3-] and pH, find CT
35

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36

36

18
 At pH 6.7 and [HCO3-] = 7.72mM,
what is total carbonate concentration?
• From the alpha table, at pH 6.7,
1 = [HCO3-]/CT = 0.715129
Hence, CT = [HCO3-]/1
= 7.72e-3M/ 0.715129 = 1.08e-2M

Plotting the pC-pH diagram. Look at equations 1, 2,

and 3 & make approximations. Let’s do this for a
closed carbonate system (H2CO3).
pKa1 = 6.3, pKa2 = 10.3, CT = 1e-3M
37

37

Plotting the pC-pH diagram for H2CO3

• Rearranging eq. 1:
[H2A] = CT / (Ka1Ka2 /[H+]2 + Ka1/[H+] + 1)

pH > pKa2 > pKa1, [H2A] ≈ CT[H+]2/Ka1Ka2

p[H2A] = pCT - pKa1-pKa2 + 2pH, slope of 2
pKa1< pH < pKa2, [H2A] ≈ CT[H+]/ Ka1
p[H2A]= pCT - pKa1 + pH, slope of 1
pH < pKa1 [H2A] ≈ CT, slope of zero
p[H2A] = pCT
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38

19
 Plotting the pC-pH diagram for H2CO3
• Rearranging eq. 2:
[HA-] = CT / ([H+]/ Ka1 + 1 + Ka2/[H+])

pH > pKa2: Ka2>>[H+] [HA-] ≈ CT[H+]/Ka2

p[HA-] = pCT - pKa2 + pH, slope of 1
pKa1< pH < pKa2, [HA-] ≈ CT
p[HA-]= pCT slope of zero
pH < pKa1, [HA-] ≈ CTKa1/ [H+]
p[HA-]= pCT + pKa1 - pH, slope of -1
39

39

Plotting the pC-pH diagram for H2CO3

• Rearranging eq. 3:
[A2-] = CT / (1 + [H+]/ Ka2 + [H+]2/Ka1Ka2 )

pH > pKa2 Ka2>>[H+] [A2-] ≈ CT

p[A2-] = pCT, slope of zero
pKa1< pH < pKa2 [A2-] ≈ CTKa2/[H+]
p[A2-] = pCT + pKa2 - pH, slope of -1
pH < pKa1 [A2-] ≈ CTKa1Ka2/[H+]2
p[A2-] = pCT + pKa1 + pKa2 - 2pH, slope of -2

40

40

20
 pC-pH diagram for 1e-3M H2CO3
pH

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0

2
CT
4 H2CO3 HCO3- CO32-

6
pC

10

12

14

Note change in slopes from 0 to 1 to 2.

41
PC: [H+] = [HCO3-] + 2[CO32-] + [OH-]

41

Solving the Equilibrium Problem

Graphically
What is the pH of a 1 mM solution of
NaHCO3?
• Species:
– Na+, H2CO3, HCO3-, CO32-, H+, OH-
• Proton Condition
– how protons have changed partners since
beginning (from starting materials)

[H2CO3] + [H+] = [CO32-] + [OH-]

use the graph to solve this. Solution is the highest intersection.
Double check in the MB/CB equation. 42

42

21
 pC-pH diagram for 1e-3M NaHCO3
[H2CO3] + [H+] = [CO32-] + [OH-] Proton Condition
pH

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0

2
CT Na+
4 H2CO3 HCO3- CO32-

6
pC

10

12

14 43

43

Solving the Equilibrium Problem

Graphically
What is the pH of a 1 mM solution of Na2CO3?
• Species: Na+, H2CO3, HCO3-, CO32-, H+,
OH-
• MB: CT = [H2CO3] + [HCO3-] + [CO32-]
[Na+] = 2CT
• CB: [Na+] + [H+] = [HCO3-] + 2[CO32-] + [OH-]

substitute for [Na+] and [CO32-] in CB

2[H2CO3] + 2[HCO3-] + 2[CO32-] + [H+] = [HCO3-] +
2[CO32-] + [OH-]

2[H2CO3] + [HCO3-] + [H+] = [OH-] Proton Condition

44

44

22
 pC-pH diagram for 1e-3M Na2CO3
2[H2CO3] + [HCO3-] + [H+] = [OH-] Proton Condition
pH

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0

2
Na+
CT
4 H2CO3 HCO3- CO32-
6
pC

10

12

14
45

45

Titration of a Diprotic Acid/Base System

Charge Balance before Titration Begins: NaOH
[H+] = [HCO3-] + 2[CO32-] + [OH-] CB

Charge Balance after Titration Started: H2CO3, CT

[Na+] + [H+] = [HCO3-] + 2[CO32-] + [OH-]

Mass Balance for Na+

[Na+] = CB

And

CB = [HCO3-] + 2[CO32-] + [OH-] – [H+]

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23
 Other Polyprotic Acid/Base Systems of Interest
Orthophosphoric Acid: H3PO4

Arsenic acid: H3AsO4

Ethelendiaminetetraacetic acid: EDTA, H4Y

Pyrophosphoric acid: H4P4O7

Dichromic acid: H2Cr2O7

Chromic acid: H2CrO4

Oxalic acid: H2C2O4

Succinic acid: H2C4H4O4 47

47

Open Systems

48

48

24
 Open vs Closed Systems

Exchange of Energy
Exchange of Energy and Mass

CLOSED SYSTEM OPEN SYSTEM

49

49

Examples of Open and Closed Systems

in Natural Waters
And Engineered Systems

Natural Aquatic Systems

Open: Rain Droplets, Surface Waters, Vadose Zone
Closed: Groundwater (spacially disconnected)

Engineered Systems:
Open: Anaerobic Digestor
Closed: Lime Softening Process (kinetically
disconnected)

50

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25
 Open System

CO2(g)

The equilibrium for the reaction:

CO2(g) + H2O = H2CO3(aq)

H2CO3(aq) K H = 10−1.5

2 Phase open system

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51

H2CO*3 = KHPCO2 = 0CT

HCO-3 = CT 1 =  1 KHPCO2 = Kal KHPCO2

0 H+

CO=3 = CT 2 =  2 KHPCO2 = KalKa2 KHPCO2

0 H+ 2
1 K1  2 K1 K 2
= =
Remember that  0 [H ]
+ ,  0 [ H + ]2

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26
 pKa1 pKa2
pH
pH
0 01 12 2 3 3 44 55 66 77 88 99 10
10 11 1213
11 12 1314
14
0 0
1 1
2 2
3 CT
3 4
H2CO3
4 5 H2CO3
5 6
H
6 7
pC

OH
pC

7 8
8 9 HCO3-
9 10 CO32-
10 11 TOTAL
11 12
13
12 14
13
14
53

53

Comparison of Three Significant

Open Systems

Ambient Air: PCO2 = 10-3.5 atm

Soil Vadose Zone: PCO2 = 10-3 to 10-1 atm

Anaerobic Digestors: PCO2 = 0.3 atm

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27
 Open System (Air, Soil gas, Digestor)
pH
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0
1
2 Digestor
3
4
Soil gas
5 Air
6
[H2CO3]
pC

7
8
9
10
11
[HCO3-]
12
[CO32-]
13
14
Air PCO2= 10-3.5 atm
Soil gas PCO2= 10-2 atm
Digestor PCO2= 0.3 atm 55

55

Open System

NH3(g)

NH3(g)  NH3(aq)

[ NH 3 (aq)] = K H PNH 3
NH3(aq)
K H = 28.6
2 Phase open system
PNH 3 = 3.5 10 −6
56

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28
 Ammonium-Ammonia System

NH4+ = NH3 + H+

Ka = [H+][NH3]/[NH4+] = 5.62 x 10-10

[NH3] = α1NT = KHPNH3

[NH4+] = αoNT

NT = [NH4+] + [NH3]
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57

Open System pH
pK
0 1 2 3 4 5 6 7 8 9 10 11a 12 13 14
pC
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
1 0
2 1 NT
3 2
NH3 3
4 NH3
4
5 5
6 6
pH
pC

7
7
8 NH4+
8 9
9 10
10 11
12
11 13
12 14
13
14 58

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29
 Closed System
pH
[H]
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0
[OH]
[NH4+]
1 [NH3]

4
NH4+ NH3
5

6
pC

10

11

12

13

14
59
MonoProtic Acid (HA)

59

Open System

pH
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0
1
2
3
4
5 [H2S]
6
pC

7
8
9 [HS-]
10
11
12
13 [S2-]
14

60

60

30