Module 4

Chemical Equilibria (Ch. 3.1-3.7, 3.9)

• Importance of equilibrium chemistry in Civil

Engineering Definition of
• Equilibrium constants (Ch. 3.1-3.4)
• Acid-Base Reactions (Ch. 3.7)
• Solubility of Gases in Water (Ch. 3.5-3.6)
• Dissolution/Precipitation of Solids (Ch. 3.9)
• The Carbonate System
 Chemical Equilibria

• Knowledge of equilibrium chemistry required

– To understand the fate and transport of organic
and inorganic compounds in the environment
– For physical-chemical treatment of wastewater
and contaminated sites
– Stability and durability of constructed structures
 Chemical Effects on Construction Materials
• Corrosion of metal structures: Oxido-reduction attack

Pier losing corroded metal Pitted support beam Degraded steel junction
http://www.chicagoclout.com/weblog/archives/2007/09/mayor_dale http://www.flickr.com/photos/aamirjaffar/5653237014/sizes/z http://billymaclellan.blogspot.ca/2011/05/rusted-bridge-
y_give_wrecked_up_br.html /in/photostream/ 2.html

• Concrete degradation and rebar corrosion: acid attack

2006 2007 2008 2009

Champlain Bridge Exposed rebars Pier losing concrete

http://tvanouvelles.ca/lcn/infos/regional/archives/2011/03/20110318- http://www.nachi.org/inspecting-visible-masonry.htm http://stainlessrebar.com/stainless-rebar-is-cost-
092951.html effective/a-look-at-corrosion/
 Chemical Effects on Construction Materials
• Limestone weathering of monuments: acid attack

Before After
Headstone in cemetary Statue around a cathedral
http://plantandsoil.unl.edu/pages/informationmodule.php?idinforma http://www.sciencedirect.com/science/article/pii/S0964830500001
tionmodule=1130447023&topicorder=5&maxto=7&minto=1 098

• Concrete degradation in sewer: gas-acid attack

Not degraded Falling material without Notice deep marking on

cementitious properties concrete
 Degradation Process of Concrete in Sewers:
Gas-Acid Attacks
Microbial oxydation H2SO4
Degradation of
of H2S to H2SO4 concrete in pipes
(strong acid)

H2S(g)

Transfer of H2S from

wastewater to headspace.

H2S / H2SO4
Microbial reduction of S2– / SO42–
H2SO4 in H2S in
wastewater. Emond, Andrew, Undermontreal.com decarie_junction.
2006-2011, http://www.undermontreal.com/sewers-ville-st-
laurent/ (accessed November 2nd, 2011)
From Emilie Hudon
Limitation to Chemical Equilibrium Analysis

– Environmental conditions are complex

(dynamic changes)
– For some reactions, equilibrium may only
be achieved very slowly (centuries)
– Lack of accurate equilibrium constants for
many important natural reactions

• Useful for predictions as long as limitations

are understood
Chemical Equilibria in Environmental Systems
• Acid-Base Reactions
• Solubility of Gases in Water (air-water partitioning)
• Solubility Product (Precipitation/dissolution)
HA (g)

HA (aq)

H+(aq)+A−(aq)

A−(aq)+Cation+(aq) Solid
General Concepts of Chemical Equilibrium
Analysis
• General equation
aA  bB  dD  eE

K
D E
d e Equilibrium Constant
G   RT ln K
o
(K)
A B
a b
(point of equilibrium)
• {A}=[A]×γ
• For dilute systems, γ (activity coefficient) = 1
• Activity of water and solids: 1
• Logaritmic notation
[ X ]  10 pX ; pX   log[ X ]
 General Concepts of Chemical Equilibrium
Analysis

aA  bB  dD  eE
• Compare Q (reaction quotient in current conditions)
and K (equilibrium constant)

Q
D  E 
d e
 Qat equilibrium  K
A B
a b

• If Q<K, reaction will proceed to the RIGHT until equilibrium

• If Q>K, reaction will proceed to the LEFT until equilibrium
Chemical Equilibria in Environmental Systems
• Acid-Base Reactions
• Solubility of Gases in Water (air-water partitioning)
• Solubility Product (Precipitation/dissolution)
HA (g)

HA (aq)

H+(aq)+A−(aq)

A−(aq)+Cation+(aq) Solid
 Water Is an Acid
• Dissociation of water

H 2O  H   OH
H OH   K
 

H 2O w

H OH   K
 
w  110 14
at 25 C o

Holds true no matter what the source of H+ and OH-

H   10
  pH
pH   log H   

Neutral solution (25 °C): H    OH   10

  7
; pH  7
 The pH scale: pH of different solutions

Solution:

log[H+]
[H+]

Solution:

pH

Solution:
 Definitions of Acids and Bases
Base: compound that can accept H+
Acid: compound that can release H+
 
HA  B  A  HB
• Water reacts with acids and bases
 
Base: B  H 2O  HB  OH
H++H2O
Acid: HA  H 2O  H 3O   A 
HA  H   A  shorthand 
Ka 
H A 
 
Acid dissociation
pK a   log K a
HA constant (Ka)
 Acid-Base Equilibria:
Concentration of Dissociated [A−] vs. Non-dissociated [HA] acid
• Equilibrium concentrations varies with pH

HA  H   A 

H A 
 
LOG{Proportion of Dissociated
and Non-Dissociated Acid (A)}

Ka
HA

[HA] [H+] [A−]

+
[H ]
 Acid-Base Equilibria:
Concentration of Dissociated [A−] vs. Non-dissociated [HA] acid
• Equilibrium concentrations varies with pH
• pKa: pH where [A−] = [HA]; 50% dissociated
HA  H   A 

H A 
 
pK a   log K a
LOG{Proportion of Dissociated
and Non-Dissociated Acid (A)}

Ka
HA

[HA] [H+][A−]

+
[H ] [H+]
 H A 
Strength of Acids  
– Strong Acid Ka 
HA
• strong tendency to dissociate
pK a   log K a
• high Ka; low pKa
• Can typically assume complete dissociation
• ex: sulfuric acid (H2SO4), hydrochloric acid (HCl)
– Weak Acid
• weak tendency to dissociate
• low Ka; high pKa
• Cannot assume complete dissociation
• ex: acetic acid (CH3COOH), carbonic acid (H2CO3)
 Multiprotic Acids
• Several acid protons can be found on an acid molecule
• Monoprotic acid: 1 proton (e.g., nitric, hydrochloric, acetic)
• Diprotic acid: 2 protons (e.g., sulfuric, carbonic)
• Triprotic acid: 3 protons (e.g., phosphoric, citric)
Related to Table 3.5 pKa: pH at which 50% acid is dissociated
 Carbonic Acid: a Di protic acid
Defining alpha’s
 HCO 3( aq ) 
H 2 CO 3( aq ) 
K a1
 CO 32(aq )
Ka 2

H+ H+
    
C t,CO3  H 2 CO 3( aq )  HCO 3( aq )  CO 32(aq ) 
1 
HCO 

3( aq )
LOG{Proportion of Dissociated
and Non-Dissociated Acid (A)}

C t,CO3

0 
H CO
2 3( aq ) CO 
2
3( aq )
C t,CO3 2 
C t,CO3
 Derivation of Alpha’s in Function of pH
How to follow the ACID/BASE concentrations? (1)
CH3COOH  CH3COO  H 

C t,CH3COO  CH 3COOH   CH 3COO  
0 
CH3COOH

CH3COOH  Ka 
 1   pH 
1

CH3COOH  CH3COO  C t,CH3COO  10 

1 
CH3COO  

CH3COOH  CH3COO  

1 
CH3COO   10  1
  pH
1

 
C t,CH3COO  Ka 
 Derivation of Alpha’s in Function of pH
How to follow the ACID/BASE concentrations? (2)
1. Do a sum of the dissolved acid (dissociated or not)
CH 3COOH  CH3COO  H 

C t,CH3COO  CH 3COOH   CH 3COO  
2. Determine the proportion of the dissociated acid
species in function of pH (for acetic acid: α0 and α1)
Ka 
CH3COO H    Derivation of α’s
CH3COOH

C t,CH3COO  CH 3COOH  CH 3COO  
0 
CH3COOH  1  Ka 
1

 10 pH 
C t,CH3COO 

1 
CH3COO   10
-  pH

 1
1


C t,CH3COO  Ka 
 Derivation of Alpha’s in Function of pH
How to follow the ACID/BASE concentrations? (3)

0 
CH3COOH 
 1
Ka 
1

1 
CH3COO  10

-  pH

 1
1

 10 pH  
C t,CH3COO  C t,CH3COO  Ka 


C t,CH3COO  CH 3COOH  CH 3COO   Ka 
CH3COO H 
 

CH3COOH
 Application of Alpha Equations
Quick Calculation of Acids/Bases Concentrations
pK a1  6.35 pK a 2 10.33
H 2 CO 3( aq )   HCO 3( aq )    CO 32(aq )
H+ H+
• The total concentration of CO3 is 5 mM
• The pH is 9
• What are the concentrations of H2CO3, HCO3, CO32 ?

  
C t,CO3  H 2 CO 3( aq )  HCO 3( aq )  CO 32(aq )   
H   H K
 2 
a1  K a1 K a 2 
0  C H 2CO3 
 H   2

 H   H K  K K 
t ,CO3  2 
 
a1 a1 a2

1  HCO  H K
 
3 a1
C  H   H K  K K 
 2 

t ,CO3

 
a1 a1 a2

 2  CCO   
2
3 K K a1 a2

 H   H K  K K 
t ,CO3  2  
 
a1 a1 a2
Why Are Acid-base Reactions So Important
in Environmental Engineering?

– Aquatic forms of life sensitive to small pH

changes (waste must be neutralized)
– pH can affect mobilization of pollutants in the
environment
– pH can be manipulated to drive contaminants
out of solution before effluent is released
Example of Technology Based on ACID/BASE:
Removal of NH3 from Wastewater by Stripping

 
NH 3  H 2 O  NH 4  OH

Ammonia gas: Ammonium ion:

less soluble more soluble

How does pH affect this reaction?

Example of Technology Based on ACID/BASE:
Removal of NH3 from Wastewater by Stripping

Lime (CaO) added

to wastewater
Example of Technology Based on ACID/BASE:
Removal of NH3 from Wastewater by Stripping
off-gas
Air Stripping Tower treatment

Packing
material

contaminated water

air

blower pump
treated water
 Important Properties of Water

• Water dissociation constant: Water dissociates in

ions H+ and OH−
– 𝐾𝑊 = 𝐻 + × 𝑂𝐻 − = 10−14

• Electroneutralinity of water: the concentration of

positive charges equal the concentration of negative
charges at all times.
– Thus, charge balance can be used in calculations
෍ 𝐵𝑐+ × 𝑐 𝑗 =෍ 𝐴𝑐− × 𝑐 𝑖
𝑗 𝑖

𝑒. 𝑔. : 𝑁𝑎+ × 1 + 𝑀𝑔2+ × 2 + 𝐻+ × 1 = 𝑂𝐻− × 1 + 𝐶𝑙 − × 1 + 𝑆𝑂42− × 2

 Problem: Calculate the pH of a Solution
Solving Using only Solution Constituents (1)
• Lets calculate the pH a solution of 5 mM of HCl (a strong acid)

HCl  Cl  H 
Ka 
Cl H   10
 
3

HCl
Steps
C
1) Total concentration of acids: t,Cl  HCl   Cl 
 

2) Charge balance:
H 2O  HO   H 
 Problem: Calculate the pH of a Solution
Solving Using only Solution Constituents
• Lets calculate the pH of vinegar, a solution of 5% (w/v) of acetic
acid (a weak acid)
CH 3COOH  CH3COO  H  
Ka 
CH COO H   10
3
 
 4.76

CH 3COOH

0 
CH3COOH 
 1
Ka 
1

1 
CH3COO -


10 pH 
 1
1

 10 pH 
C t,CH3COO  C t,CH3COO  Ka 
Steps
1) Total concentration of acids: C t,CH3COO  CH 3COOH   CH 3COO

 

2) Charge balance:
H 2O  HO   H 
 Problem: Calculate the pH of a Solution
Solving Using only Solution Constituents
• Lets calculate the pH of vinegar, a solution of 5% (w/v) of acetic
acid (a weak acid)

C t,CH3COO  CH 3COOH   CH 3COO 
 Ka 
CH COO H   10
3
 
 4.76

CH 3COOH

Quadratic equation
 b  b 2  4ac
x
2a
Chemical Equilibria in Environmental Systems
• Acid-Base Reactions
• Solubility of Gases in Water (air-water partitioning)
• Solubility Product (Precipitation/dissolution of solids)
HA (g)

HA (aq)

H+(aq)+A−(aq)

A−(aq)+Cation+(aq) Solid
 Solubility of Gases in Water

Inject Air-water partitioning

Molecules
• Direction of the net transfer
Air • Dissolution of gases
Air-phase – From air to water
molecules
CO 2 ( g ) net
transfer
 CO 2 (aq)

• Volatilization of chemicals
Dissolved (e.g., tricholoroethylene)
molecules
– From water to air
Water
TCE ( g )   TCE (aq)
net transfer
 Gas-Water Partitioning

• KH is an equilibrium constant called Henry’s

Law Constant (valid for ideal systems)

Concentration of pollutant in water

KH 
Partial pressure of pollutant in air (concentration)

CO 2 ( g )  CO 2 (aq )

KH 
CO  
Dissolved Concentration 
2 ( aq )

PCO2 ( g ) Pg
Solubility of Gases in Water with Temperature
• Values of KH [(mol/L) ∕atm] for CO2 and O2 at different
temperatures (Table 2.4)
• Solubility decreases with increasing temperature
Temperature
K H ,CO 
CO 2 ( aq ) 
K H ,O 
O 2 ( aq ) 
(oC) PCO ( g )
2 2
PO ( g )
2 2

(mol/L) ∕atm (mol/L) ∕atm

0 0.076 0.0022
5 0.064 0.0019
10 0.053 0.0017
15 0.045 0.0015
20 0.039 0.0014
25 0.033 0.0013
 Problem: Solubility of a Gas
Infinite Source vs. Self-contained Systems
Problem (infinite source of gas in system)
The water in a beaker has reached
equilibrium with the O2 in the air. What is
the concentration in the water?
Temp. = 25 °C and KH = 1.3×10−3 M/atm
Ptotal=1 atm; PO2=0.21 atm

Air

Water
 Problem: Solubility of a Gas
Infinite Source vs. Self-contained Systems
Problem (self-contained system)
Inject
100 mL of pure methane (CH4) is
Molecules
injected in a 2 L bottle containing 1 L of
water. What is the concentration of CH4
in the water at steady state?
Temp. = 25 °C and KH = 1.3×10−3 M/atm
Pair=1 atm; PCH4 in injector=1 atm
Air

Water
Gas-Water Partitioning: Caviats and Limitations

• KH expressed in many different ways and different units

– Be careful with tables, check the units
• Only valid for equilibrium conditions
• Systems rarely at equilibrium
– Excess or deficiency of dissolved gas
– Will tend towards equilibrium
– Can predict the direction of change
Chemical Equilibria in Environmental Systems
• Acid-Base Reactions
• Solubility of Gases in Water (air-water partitioning)
• Solubility Product (Precipitation/dissolution of solids)
HA (g)

HA (aq)

H+(aq)+A−(aq)

A−(aq)+Cation+(aq) Solid
 Precipitation-Dissolution of Solids

• Significance in environmental engineering:

– Scale formation in pipes
2 2
CaCO3 ( s )  Ca ( aq )  CO 3 ( aq )

- Phosphorus removal from wastewater

2PO 3-
4 ( aq )  Al2 SO 4 3  2AlPO4 ( s )  3SO 2
4 ( aq )

alum
 Precipitation-Dissolution of Solids

• Significance in environmental engineering:

– Removal of toxic metals from water or wastewater
MeOH 2 ( s )  Me 2
( aq )  2OH 
( aq )

Me: metal, e.g. Cu2+

− Fluoridation of drinking water

CaF2 ( s )  Ca 2 ( aq )  2F ( aq )
 Solubility Products

• Reaction conventionally written in dissolution direction

b a
A a Bb ( s )     aA
precipitation
dissolution
(aq)  bB
(aq)

Solid precipitate Ionic components

K
A  B 
b a
(aq)
a b
(aq)

A B a b(s)


K sp  A  B 
b a
(aq)
a b
(aq) Solubility product
 Solubility Problems
Precipitation vs Dissolution: When pH has no impact
• Ab is the conjugate base of a strong acid (pKa<3)
b a
A a Bb ( s )     aA
precipitation
dissolution
(aq)  bB (aq)

K sp  A   B 
b a
(aq)
a b
(aq)

• Dissolution: concentrations increase

• Precipitation: concentrations decrease
• In both cases, Ksp is met at equilibrium

Pose x (amount dissolved or precipitated) to solve

A 
b
 
b
 A(aq)  ax
(aq) at eq initial
K sp  A  b a
 B  a b

B 
a
(aq) at eq  B 
a
(aq) initial b x
(aq) at eq . (aq) at eq .
 Solubility Problems
Precipitation vs Dissolution: When pH has no impact
EXAMPLE PROBLEM
A solution is in contact with lead(II) fluoride and it reached equilibrium. If there
was no lead fluoride dissolved before the first contact, how much lead to you
expect to be in solution? (F is the conjugate base of HF, a strong acid)

PbF2 ↔ Pb2+ + 2F − 𝐾𝑠𝑝 = 2.7 × 10−8

 Solubility Problems
When Hydroxide (OH) Precipitates
pH is constant (we restrict ourselves to this type of problems)

• OH− is part of the reaction

BOH a ( s )   
precipitation
   
dissolution
 B a
(aq)  aOH 
 
a 
(aq) K sp  B(aq) OH (aq) 
a

e.g. : MgOH 2 ( s )  2
 Mg (aq) 
 2OH(aq)
– Constant pH mean constant [OH−]
OH 
(aq) at eq  10 14 pH

Pose x (amount dissolved or precipitated) to solve

B 
a
(aq) at eq  
a
 B(aq) initial
x
 Solubility Problems
When Hydroxide (OH) Precipitates
pH is constant (we restrict ourselves to this type of problems)
EXAMPLE PROBLEM
In the previous problem of the dissolution of PbF2 , you predicted that
1.9 × 10−3 𝑀. Assume that the pH of this solution is 7. At high pH, lead readily
precipitates in the form of lead hydroxide (𝑃𝑏 𝑂𝐻 2 ). If the pH is raised from 7
to 8.5 and maintained constant, how much lead will precipitate?

Pb 𝑂𝐻 2 ↔ Pb2+ + 2OH − 𝐾𝑠𝑝 = 1.2 × 10−15

 Solubility Problems
When Conjugate Base of a Weak Acid Precipitates
pH is constant (we restrict ourselves to this type of problems)
• Ab− is the conjugate base of a weak acid
A a Bb ( s )   
precipitation
   
dissolutio n
 aA b
(aq)  bB a

b a
(aq) K sp  A(aq)
a
 
B(aq)
b

2 
e.g. : CaCO3( s ) 
 Ca (aq)  CO 32(aq)
– Constant pH mean constant alpha’s
 HCO 3( aq ) 
H 2 CO 3( aq ) 
K a1
 CO 32(aq )
Ka 2

 
+ +
H H  K a1 K a 2 
A(aq) at eq   ?Ct ,A,at eq.
b
e . g .,     pH 2 
 10  pH K a1  K a1 K a 2 
2
10
– However, Ct,A will change ൫𝐶𝑡,𝐴 =

Ct ,A,at eq  Ct ,A,initial  a  x
B a
(aq) at eq  
a
 B(aq) initial
b x
 Solubility Problems
When Conjugate Base of a Weak Acid Precipitates
pH is constant (we restrict ourselves to this type of problems)
EXAMPLE PROBLEM
How much calcium carbonate will dissolve in water if the pH is kept
constant at 9?
2 
CaCO3( s ) 
 Ca (aq)  CO 32(aq) 𝐾𝑠𝑝 = 3.3 × 10−9

pK a1  6.35 pK a 2 10.33
H 2 CO 3( aq )   HCO 3( aq )    CO 32(aq )
H+ H+

 K a1 K a 2 
 2    pH 2  pH 
10  10 K a1  K a1 a 2 
K
 Predict the Changes in Solubility (Gas And Solids)
with Changes in Temperature?
G equation
• Careful, it is not a direct application of
NO: G  G o  RT ln K 

• Change in solubility (gas and solids) with changes in

temperature is dependent on the reaction’s enthalpy ( H o).
• Van’t Hoff equation (derivation)
G o  H o  TS o   RT ln K 

K1 H reaction
o
1 1
ln    
K2 R  T2 T1 
Chemical Equilibria in Environmental Systems
• Acid-Base Reactions
• Solubility of Gases in Water (air-water partitioning)
• Solubility Product (Precipitation/dissolution of solids)
HA (g) The Carbonate System

HA (aq)

H+(aq)+A−(aq)

A−(aq)+Cation+(aq) Solid
 The Carbonate System
• Importance and Definition
– Most important acid-base system in environment
– Controls pH in natural waters
– Controls pH in water and wastewater treatments
– Buffering system for water treatment: Alkalinity
– Aqueous components:
Dissolved carbon dioxide CO 2(aq)
Carbonic acid H 2CO3(aq)
Bicarbonate ion HCO3 ( aq )
Carbonate ion CO 32 ( aq )
 The Carbonate System

CO 2 ( aq )  H CO   K
2 3( aq ) P
H g ,CO 2  
H 2 CO *
3( aq ) 

Gas dissolution: CO 2 ( g )  CO 2 ( aq )  H 2 CO 3( aq )
H2O(l)

Acid/Base Diss.:  HCO3( aq ) 

H 2 CO3( aq ) 
K a1
 CO32(aq )
Ka 2

H+ H+

CO32(aq )  Ca (2aq ) 


K
Precipitation: sp
CaCO3(s)

Concept of H2CO3*
• It is hard to measure separately CO2(aq) and H2CO3(aq).
• Thus, define a combined formula: {CO2(aq) + H2CO3(aq)}=H2CO3*
 The Carbonate System
 HCO 3( aq ) 
H 2 CO 3( aq ) 
K a1
 CO 32(aq )
Ka 2

H+ H+
 The Carbonate System
Open vs. Closed Carbonate System
Gas dissolution: CO 2 ( g )  H 2 CO*3( aq )
H2O(l)
Acid/Base Diss.:  HCO3( aq ) 
H 2 CO*3( aq ) 
K a1
 CO 32(aq )
Ka 2

H+ H+
2 2
 Ca 
 CaCO 3(s)
K sp
Precipitation: CO 3( aq ) ( aq )

Open or Closed Carbonate Systems

• Determined by the speed of the gas/water exchanges relative to
the speed of reactions affecting the acid-base equilibrium
• Open system: gas/water exchanges faster than other reactions
→ [H2CO3*]=KH,CO2PCO2 is always true in problem
• Closed system: gas/water exchanges slower than other reactions
→ No new Ct,CO3 from air
 The Carbonate System
Open vs. Closed Carbonate System
CO 2( g )
H2O(l)
H+ H+
H 2 CO *3( aq ) HCO 3( aq ) CO 32(aq )
Acid/Base Equilibrium ALWAYS VERY FAST (1) 2
Ca ( aq )
(2) Growth of bacteria:
CaCO3(s)
H2S + 2O2 → H2SO4 ↔ 2H+ + SO4 2–

Determination of open vs. closed system

• Compare rates of pH change mechanism and gas exchange rates
1. Precipitation
• Precipitation is faster than gas exchange→ CLOSED SYSTEM
(if one considers the small interface area compare to volume)
2. Growth of bacteria producing acid (H+)
• Growth is slower than gas exchange → OPEN SYSTEM
 Summary of Carbonate System
Defining Classes of Problems and Approaches

Solids Involvement Open System Closed System

(dissolution or
precipitation)

No solids • [H2CO3*]=KH,CO2PCO2 • [H2CO3*]: vary with pH

• Ct,CO3: vary with pH • Ct,CO3: constant despite
pH varying
With solids • [H2CO3*]=KH,CO2PCO2 • [H2CO3*]: vary with pH
and solids in solution
• Ct,CO3: constant if pH • Ct,CO3: vary with solids
constant; vary with pH only in solution only