Updated: 1 February 2019 Print version

Lecture #6
Kinetic and Thermodynamics: Some
Thermo Fundamentals
(Stumm & Morgan, Chapt.2-3 )

(Benjamin, Chapt 2)
David Reckhow CEE 680 #6 1
Chapt 2: Basics
 Thermodynamics
 Will tell you
 which reactions are favorable or “Possible”
 composition of systems at equilibrium Sets limits
 Won’t tell you
 how quickly the reactions proceed
 good for systems with constant P & T
 Air: 1.0 atm at sea level
 Water: 1.0 atm for each additional 10.7 m of water
 Earth: wt of overlying rock and soil
 Governing property @ const. T&P is the Gibbs Free Energy
 for constant T&V, it is the Helmholtz Free Energy

David Reckhow CEE 680 #6 2

Thermodynamics: Examples
 Removal of P from wastewater by Alum
 is it possible?
 What is best pH? Yes
 What is the final P concentration?
 How much is removed in treatment system? No
 Ammonia stripping
 best pH?
 Acid rain
 pH of “pure” rainwater?

David Reckhow CEE 680 #6 3

Open & Closed Systems

 Closed Systems
 No significant flux of material into or out of system
 Like an isolated beaker of water
 Steady state condition is the true chemical
equilibrium
 Open systems
 Mass movement across system
boundary from or to outside world
 More realistic, but more complicated
 Steady state condition may not be true chemical
equilibrium, due to continuous perturbation from
outside

David Reckhow CEE 680 #6 4

Laws of Thermodynamics Universe

System
 1st Law
 Conservation of energy
 best you can hope for is to “break even”
 dE=dq-dw E = internal energy
 2nd Law q = heat transfer to the system
w = work done by the system
 Entropy of the universe tends to increase
 you can’t even “break even”
 dSsys > dq /T, for irreversible processes
 dSuniv = dSsys + dSsurr ≥ 0
And since: dSsurr = -dq/T
 3rd Law
 Entropy is zero for a perfect crystal at absolute zero

David Reckhow CEE 680 #6 5

Combining 1 st & 2nd Laws
 Internal Energy Change for reversible processes
 dE = dq – dw And since: dSsys = dq /T
 dE = TdSsys – dw
When only pV work is done on
 dE = TdSsys – pdV
the surroundings
 But for a system not at equilibrium that is undergoing an
irreversible process, entropy must increase beyond dq/T
 dE < TdSsys – pdV
dSsys = diS + dq /T
 dE – TdSsys + pdV <0
 And taking into account the entropy increase, diS, we can
maintain the equality
 dE = TdSsys – TdiS – pdV

David Reckhow CEE 680 #6 6

Enthalpy
 A fundamental thermodynamic variable
 enthalpy change is equal to heat of reaction (for
systems at constant pressure)
 ∆H<0, heat is given off dH = TdS + V dp
 exothermic dH = dq + V dp
 ∆H>0, heat is absorbed dH = dq, for constant
 endothermic pressure processes with no
 ∆H can be calculated from external work (w=0)
standard enthalpies of formation (∆Hof )
 available in many texts

 e.g., Snoeyink & Jenkins, Table 3-1 ∆

H = ∑ν i H
o ∆ o
f

David Reckhow CEE 680 #6 7

Example
 Evaporation of water H2O(g

 H2O(l) = H2O(g) )

∆
H o = ∑ν i ∆ H of H2O(g H2O(l)
H2O(l)

= (1mole )(− 57.80 mole ) + (− 1mole)(− 68.32 mole )

)
kcal kcal

= +10.52 kcal
 ∆H>0, heat is absorbed
 endothermic
 However, this does not tell us if the reaction is
favorable, or proceeds spontaneously
 to answer this we need to know the entropy change

David Reckhow CEE 680 #6 8

Thermodynamic Constants for Species of Importance in Water
Chemistry (Table 3-1 from Snoeyink & Jenkins) Part I

∆ o ∆ o ∆ o ∆ o
Species Hf Gf Species Hf Gf
kcal/mole kcal/mole kcal/mole kcal/mole
+2
Ca (aq) -129.77 -132.18 CO3-2 (aq) -161.63 -126.22
-
CaC03(s), calcite -288.45 -269.78 CH3COO ,
-116.84 -89.0
acetate
CaO (s) -151.9 -144.4 H+ (aq)
0 0
C(s), graphite 0 0 H2 (g)
0 0
+2
CO2(g) -94.05 -94.26 Fe (aq)
-21.0 -20.30
+3
CO2(aq) -98.69 -92.31 Fe (aq)
-11.4 -2.52
CH4 (g) -17.889 -12.140 Fe(OH)3 (s)
-197.0 -166.0
H2CO3 (aq) -167.0 -149.00 Mn+2 (aq)
-53.3 -54.4
HCO3- (aq) -165.18 -140.31 MnO2 (s)
-124.2 -111.1

Conversion: 1kcal = 4.184 kJ

David Reckhow CEE 680 #6 9
Thermodynamic Constants for Species of Importance in Water
Chemistry (Table 3-1 from Snoeyink & Jenkins) Part II
∆ o ∆ o ∆ o ∆ o
Species Hf Gf Species Hf Gf
kcal/mole kcal/mole kcal/mole kcal/mole
+2
Mg (aq) -110.41 -108.99 O2 (g) 0 0
Mg(OH)2 (s) -221.00 -199.27 OH- (aq) -54.957 -37.595
NO3- (aq) -49.372 -26.43 H2O (g) -57.7979 -54.6357
NH3 (g) -11.04 -3.976 H2O (l) -68.3174 -56.690
NH3 (aq) -19.32 -6.37 SO4-2 -216.90 -177.34
NH4+ (aq) -31.74 -19.00 HS (aq) -4.22 3.01
HNO3 (aq) -49.372 -26.41 H2S(g) -4.815 -7.892
O2 (aq) -3.9 3.93 H2S(aq) -9.4 -6.54

Conversion: 1kcal = 4.184 kJ

David Reckhow CEE 680 #6 10

 A measure of a system’s
Entropy randomness
 remove the partition
and randomness
T=0
V1 , c 1 V2 , c 2 increases
 2nd law of Thermo.

T=1 ∆
S = ∑ν i S
o ∆ o
f

 Spontaneous in isolated
T=2 system
 Like water running downhill
 Or hot objects heating
colder ones
T=large

David Reckhow CEE 680 #6 11

Gibbs Free Energy
 Combines enthalpy and entropy
 1st and 2nd laws of thermodynamics
 Determines whether a reaction is favorable or
spontaneous
 Practical form is based on an arbitrary datum
 the pure and most stable form of each element at
standard state
∆ ∆ ∆ o
G = H −T S
o o

David Reckhow CEE 680 #6 12

Standard State
About:
 Standard State 1 mole/L for dissolved substances
 Conditions: 1 atmosphere for gases
 Unit activity (a=1)

 Rarely encountered in practice; but easier to base

calculations on
 State variables: ∆Go, µo
 Non-standard State
 Conditions:
 Non-unit activity, often quite low

 This is the “real world”

 State Variables: ∆G, µ

David Reckhow CEE 680 #6 13

Solving problems with G
Recall, at any T & P: G = ∑ν i µi
∆ o o

 ∆G can be calculated at 25oC from

standard gibbs free energies of But for STP, we use:
formation (Gof )
 These are essentially ∆G’s for the
G = ∑ν G
∆ o
i f
o

formation of chemical substances from

the most stable forms of their
constituent elements
 available in many texts
 e.g., Stumm & Morgan, Appendix 3
In: kJ/mole
 e.g., Benjamin, Table 2.1
 e.g., Snoeyink & Jenkins, Table 3-1 In: kcal/mole
Conversion: 1kcal = 4.184 kJ

David Reckhow CEE 680 #6 14

Ammonia Problem (1/7)
 Determine ∆Go for dissolution of ammonia in water
at 25oC
NH 3 ( g ) ↔ NH 3 (aq )
 Based on example 2.5 in text
 Two approaches
 A. Determine ∆Go directly from individual Gof ’s
 The easiest way

 B. Determine ∆Go from ∆Ho and ∆So

∆
G o = ∆H o −T ∆S o

David Reckhow CEE 680 #6 15

Ammonia Problem (2/7)
 A. Determine ∆Go directly from individual Gof ’s
 Get thermodynamic data
 from Appendix A (Benjamin) or Appendix 3 (S&M)

 Expand equation and substitute data

∆
G o = ν NH 3 ( g )G of − NH 3 ( g ) + ν NH 3 ( aq )G of − NH 3 ( aq )
∆
G = ∑ν i G
o o
f
= (−1)(−16.48) + (1)(−26.57)
= −10.09 Units are kJ/mole
Formation from the Entropy
Elements
Species Gfo (kJ Hfo (kJ So (J mol- Reference
mol-1) mol-1) 1 -1
K )
NH3(g) -16.48 -46.1 192 NBS
NH3(aq) -26.57 -80.29 111 NBS
NH4+(aq) -79.37 -132.5 113.4 NBS

David Reckhow CEE 680 #6 16

Ammonia Problem (3/7)
 B. Determine ∆Go from ∆Ho and ∆So
 Get thermodynamic data from Appendix A (or 3)
 Expand equations and substitute data

∆
H o = ν NH 3 ( g ) ∆ H of − NH 3 ( g ) + ν NH 3 ( aq ) ∆ H of − NH 3 ( aq )
∆
H = ∑ν i H
o ∆ o
f = (−1)(−46.1) + (1)(−80.29)
= −34.19 Units are kJ/mole
∆
S o = ν NH 3 ( g ) S NH + ν
S = ∑ν i S
o o
S
∆ o o 3(g) NH 3 ( aq ) NH 3 ( aq )

= (−1)(192) + (1)(111)
= −81 Units are J/mole/oK

David Reckhow CEE 680 #6 17

Ammonia Problem (4/7)
 Now combine and solve for ∆Go

∆ ∆ ∆ o
G = H −T S
o o

= (−34.19) − (273.16 + 25)(−81)(1000

1kJ
J
)
= −10.04 Units are kJ/mole
 Conclusion: reaction is spontaneous since ∆Go <0
 Lingering question: what actually happens when we’re not
at standard state conditions (i.e., when activity isn’t equal
to one)?

David Reckhow CEE 680 #6 18

Chemical Potential
 Like a Gibbs Free Energy normalized per mole

 a function of activity and temperature

 ∂G  kJ
µ i =  
kJ/mole  ∂ni T , P

µ i = µ io + RT ln ai

This term corrects for the fact that

Standard state (unit activity) we’re not at unit activity

David Reckhow CEE 680 #6 19

Example
 Activities in concentrated NaCl solution
 S&M: Example 2.3 (pg 40)

David Reckhow CEE 680 #6 20

General Condition
 And relating to the change in G for complete
conversion to products
∆
G = ∑ν i µ i and
∆
G o = ∑ν i µ io
(
= ∑ν i µ io + RT ln ai )
= ∑ν i µ io + RT ∑ν i ln ai
aCc aDd
∆
G = ∆G o + RT ln Q where Q≡ a b
a A aB

For the reaction: aA + bB ↔ cC + dD

David Reckhow CEE 680 #6 21

Ammonia problem (5/7)

 Now lets see what the ∆G is for the following non-

standard conditions
 [NH3(aq)] = 10-3 M
 pNH3 = 10-4 atm
 Now we need to determine Q
 Recall the reaction:
NH 3 ( g ) ↔ NH 3 (aq )
 So:
10 −3
1
a NH 3 ( aq )
Q= ≅ − 4 = 10
a1NH 3 ( g ) 10

David Reckhow CEE 680 #6 22

Ammonia problem (6/7) R=1.987 x10-3 kcal/mole oK
=8.314 x10-3 kJ/mole oK
 Now substitute back into the equation for ∆G

∆
G = ∆G o + RT ln Q
= −10.04 + (0.008314)(273.16 + 25) ln(10)
= −4.33 Units are kJ/mole

 Conclusion: the reaction is still spontaneous at these

non-standard concentrations
 i.e., the reaction will proceed toward the right
 Another lingering question: how far to the right will it
proceed before it reaches equilibrium and stops?
 To answer this we need to determine “K”

David Reckhow CEE 680 #6 23

Equilibrium Quotients
 at Equilibrium ∆G=0, so: 0= ∆G o + RT ln K
 and:
∆
Where K is defined as the
G = − RT ln K
o
quotient (Q) at equilibrium
= −2.303RT log K and is generally referred to
as the “equilibrium constant”
 or: aCc aDd
∆
K ≡ a b , at equilibrium
Go a A aB
log K = −
2.303RT

David Reckhow CEE 680 #6 24

Ammonia problem (7/7) R=1.987 x10-3 kcal/mole oK
=8.314 x10-3 kJ/mole oK
 To determine the equilibrium position of
ammonia dissolution, we need the equilibrium
constant, K
∆
Go
log K = −
2.303RT K = 101.76
− 10.04
=− = 57.4
2.303(0.008314)(273.16 + 25)
= 1.76
 So as we approach equilibrium, Q will approach the
value of K, which is 57.4
a1NH 3 ( aq ) 10 −3
Q= ≅ − 4 = 10
a1NH 3 ( g ) 10
David Reckhow CEE 680 #6 25
Quotients (cont.)
 more generally, for non-equilibrium conditions, we
can combine:
∆
G = ∆G o + RT ln Q
= − RT ln K + RT ln Q ∆
G = 2.303RT log Q 
 K
= RT ln Q 
 K

 and if,
 ∆G<0, (Q/K)<1, and equilibrium lies to the right
 ∆G>0, (Q/K)>1, and equilibrium lies to the left
 ∆G=0, (Q/K)=1, and system is at equilibrium

David Reckhow CEE 680 #6 26

Gibbs Energy of a System
Fig. 2.5
 G Changes as reaction Pg. 45
progresses due to changing
concentrations
 G reaches a minimum at the
point of equilibrium

∆ dG
G≡
dξ

Extent of reaction
David Reckhow CEE 680 #6 27
The Gfo Convention
 Since the Gfo values are essentially ∆G’s for the
formation of chemical substances from the “most
stable” (reference) forms of their constituent
elements
 The Gfo values for those most stable elemental forms are
zero, by definition
 Examples
 Zero-valent, Metallic Ag, Al, Fe, Mn, Pb, Zn
 graphite-C, white-P, rhombic-S
 diatomic H2, I2, N2, O2

David Reckhow CEE 680 #6 28

Simple examples ∆
Reaction Go
H2 (g) + S(s) = H2S(aq) -27.87
H2 (g) + S(s) = H2S(g) -33.56
O2 (g) + S(s) = SO2 (g) -300.2
Hg(l) + S(s) = HgS(s) -43.3
H2 (g) + ½O2 (g) = H2O(l) -237.18
O2(g) = O2 (aq) 16.32
 In all of these cases reactants have a Gfo equal to zero, i.e., they are
the reference forms of the elements
 so the ∆Go is simply equal to the Gfo of the product compound

David Reckhow CEE 680 #6 29

 S&M: Example 2.4 Fig. 2.7
 (pg 46)
Pg. 48
 Dissolution of CO2
 CO2 (g) = CO2 (aq)

∆ ∆ ∆
G = H −T S

David Reckhow CEE 680 #6 30

Hexavalent Cr
is now a big
Chromium Example (1/6) regulatory issue

Example 2.10 from (pg 111): Benjamin, 2002

David Reckhow CEE 680 #6 31
Chromium Example (2/6)

∆
Go
log K = −
2.303RT

Example 2.10 from (pg 111): Benjamin, 2002

David Reckhow CEE 680 #6 32
Chromium Example (3/6)

Example 2.10 from (pg 111): Benjamin, 2002

David Reckhow CEE 680 #6 33
Chromium Example (4/6)

Example 2.10 from (pg 111): Benjamin, 2002

David Reckhow CEE 680 #6 34
Chromium Example (5/6)

Example 2.10 from (pg 111): Benjamin, 2002

David Reckhow CEE 680 #6 35
Chromium
Example (6/6)

 Minimum
Gibbs free
energy is where
ΔGr = 0

Example 2.10 from

(pg 111): Benjamin,
2002
David Reckhow CEE 680 #6 36
Alternative Direct Calculation
𝐶𝐶𝐶𝐶2 𝑂𝑂7−2
𝐾𝐾 =
 Assume standard activity for water 𝐻𝐻𝐻𝐻𝐻𝐻𝑂𝑂4− 2
 Combine equilibrium and mass balance equations
𝐶𝐶𝐶𝐶𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 0.1 = 𝐻𝐻𝐻𝐻𝐻𝐻𝑂𝑂4− +2 𝐶𝐶𝐶𝐶2 𝑂𝑂7−2
−2
 Set bichromate = x 2 𝐶𝐶𝐶𝐶 𝑂𝑂
2 7 =0.1-x

𝐶𝐶𝐶𝐶2 𝑂𝑂7−2 0.05 − 0.5𝑥𝑥

𝐾𝐾 = 32.5 = − 2 =
𝐻𝐻𝐻𝐻𝐻𝐻𝑂𝑂4 𝑥𝑥2
32.5𝑥𝑥 2 + 0.5𝑥𝑥 − 0.05 = 0
 And using the quadratic formula

−𝑏𝑏 ± 𝑏𝑏 2 − 4𝑎𝑎𝑎𝑎 −0.5 ± 0.25 − 6.5

𝑥𝑥 = = = 0.032278
2𝑎𝑎 65
David Reckhow CEE 680 #6 37
Ionic Species & Redox
 Conventions
 Gfo = 0, for H2
 Gfo = 0, for H+
 this makes the hydrogen oxidation half reaction a
reference point for Redox
 for: ½H2 (g) = H+ + e-, ∆G = 0
 oxidations and reductions
 must be coupled
 we only concern ourselves with the differences in ∆G for the
two half reactions

David Reckhow CEE 680 #6 38

Temperature Effects on K
 Need ∆H (enthalpy change)
 ∆H < 0, exothermic (heat evolved)
 ∆H > 0, endothermic (heat absorbed)
 The Van’t Hoff Equation:
∆
H o (T2 −T1 )
log K2
K1 = 2.303 RT2T1
Log K
 recall that:

∆
H o = ∑ν i ∆ H of
1/T

David Reckhow CEE 680 #6 39

∆ ∆ ∆ o
Van’t Hoff Equation G = H −T S
o o

 Where does it come

− RT ln K = ∆H o −T ∆S o
from?
∆ ∆
ln K = − Ho
RT + R
S

∆
d ln K
dT = Ho
RT 2
K2 T2
∆
H (T2 −T1 )
∫ d ln K = ∫
o
=
K2 ∆
Ho dT
log K1 2.303 RT2T1 R T2
K1 T1

ln K2
K1 =
∆
Ho
R
(1
T1 − T12 )
David Reckhow CEE 680 #6 40
Home
Water
Heater
 Gas fired

From: Quick Guide Plumbing,

Creative Homeowner Press
David Reckhow CEE 680 #6 41
Thickness Loss of

Scale
of Scale in of Heat
Inches Transfer
Efficiency
1/16 15%
1/8 20%
1/4 39%
1/2 70%
3/4 90%
A cross section of 1 & 1/2" copper pipe Data: US National Bureau of
with a scale build-up of over 1/2" in Standards

thickness
Calcium scale formation on the inside of pipes and water heaters, on sinks, tubs, shower
doors and other water contact surfaces is a multi-million dollar problem for individuals and
businesses. A thin, one eighth inch layer of scale is such an effective insulator that it reduces
the efficiency of your water heater by 20%. This translates directly to increased energy cost
to attain the desired water temperature. Scale also increases the cost of equipment
maintenance and shortens equipment life. When these costs are added together, the price of
calcium scale is staggering

David Reckhow CEE 680 #6 42

Example Problem
 Water is at equilibrium with calcium carbonate at
25oC. It enters a house at 15oC, then is heated to
60oC in a water heater.
 Is the water supersaturated as it
 A. enters the house?
 B. leaves the water heater?

 Solution to A.
 1. Calculate ∆Go
 2. Determine K1 at 25oC
 3. Determine ∆Ho
 4. Determine K2 at 15oC

David Reckhow CEE 680 #6 43

Solution
 At neutral pH: CaCO3 (s) + H+ = HCO3- + Ca+2
 1. Calculate ∆Go
 =-140.31-132.18-(-269.78) = -2.71 kcal
 2. Determine K1 at 25oC
 ∆Go=-RTlnK = -2.303RT*logK
 -2.71=-2.303(0.001987)298*logK =-1.364logK
 log K =1.99; K=101.99
 3. Determine ∆Ho
 =-165.18-129.77-(-288.345) = -6.5 kcal
 4. Determine K2 at 15oC
 log (K2/101.99) = -6.5(288-298)/2.303(0.001987)288(298)=0.1655
 log K2 = 2.156
 K2 = 102.16
David Reckhow CEE 680 #6 44
Thermodynamic Constants for Species of Importance in Water
Chemistry (Table 3-1 from Snoeyink & Jenkins) Part I

∆ o ∆ o ∆ o ∆ o
Species Hf Gf Species Hf Gf
kcal/mole kcal/mole kcal/mole kcal/mole
+2
Ca (aq) -129.77 -132.18 CO3-2 (aq) -161.63 -126.22
-
CaC03(s), calcite -288.45 -269.78 CH3COO ,
-116.84 -89.0
acetate
CaO (s) -151.9 -144.4 H+ (aq)
0 0
C(s), graphite 0 0 H2 (g)
0 0
+2
CO2(g) -94.05 -94.26 Fe (aq)
-21.0 -20.30
+3
CO2(aq) -98.69 -92.31 Fe (aq)
-11.4 -2.52
CH4 (g) -17.889 -12.140 Fe(OH)3 (s)
-197.0 -166.0
H2CO3 (aq) -167.0 -149.00 Mn+2 (aq)
-53.3 -54.4
HCO3- (aq) -165.18 -140.31 MnO2 (s)
-124.2 -111.1

David Reckhow CEE 680 #6 45

Thermodynamic Constants for Species of Importance in Water
Chemistry (Table 3-1 from Snoeyink & Jenkins) Part II
∆ o ∆ o ∆ o ∆ o
Species Hf Gf Species Hf Gf
kcal/mole kcal/mole kcal/mole kcal/mole
+2
Mg (aq) -110.41 -108.99 O2 (g) 0 0
Mg(OH)2 (s) -221.00 -199.27 OH- (aq) -54.957 -37.595
NO3- (aq) -49.372 -26.43 H2O (g) -57.7979 -54.6357
NH3 (g) -11.04 -3.976 H2O (l) -68.3174 -56.690
NH3 (aq) -19.32 -6.37 SO4-2 -216.90 -177.34
NH4+ (aq) -31.74 -19.00 HS (aq) -4.22 3.01
HNO3 (aq) -49.372 -26.41 H2S(g) -4.815 -7.892
O2 (aq) -3.9 3.93 H2S(aq) -9.4 -6.54

David Reckhow CEE 680 #6 46

Solution (cont.)
 Repeat step #4 for 60oC.
 4. Determine K2 at 60oC
 log (K3/101.99) = -6.5(333-298)/2.303(0.001987)333(298)= -0.5
 log K3 = 1.49
 K3 = 101.49
 Compare K1 and K2 and K3
 what does this tell you about possible precipitation?
 As temp increases, solubility decreases

 This is an exothermic reaction, so rising temp drives

reaction to the left

David Reckhow CEE 680 #6 47

Le Chatelier’s Principle
 A system at equilibrium, when subject to a
perturbation, responds in a way that tends to
minimize its effect
 If ∆H>0 (endothermic), dlnK/dT >0, and K⇑ as T ⇑
 if you heat endothermic reaction they will go further to the right
 If ∆H<0 (exothermic), dlnK/dT <0, and K⇓ as T ⇑
 if you heat exdothermic reaction they will go back to the left

∆
d ln K
dT = Ho
RT 2

David Reckhow CEE 680 #6 48

Pressure & Temp. effects
 Temp
Fig. 2.8
∂ G ∆ o
 Pg. 56
  =− ∆S o
 ∂T P
 Pressure

 ∂ ∆G o  ∆ o
  = V
 ∂P T

David Reckhow CEE 680 #6 49

 To next lecture

DAR

David Reckhow CEE 680 #6 50