ACEE 219

E i
Environmental
t l Chemistry
Ch i t

Week
W k3
March 16, 2010
Innovation Hall 127
ACEE 219 Spring 2010 HDP 1
 Review of the Last Class

1. Chemical kinetics.
2 Rate laws (O
2. (O, 1st, 2nd order reactions).
reactions)
3. Arrhenius equation (temperature dependence on
kinetic).
kinetic)
4. Estimating reaction constant with different
temperature.
temperature
5. Biological kinetics (Michaelis-Menten and Monod
equations)

ACEE 219 Spring 2010 HDP 2

 Kinetics & Reactor Design

Reactants Products

Plug Flow Reactor

Reactants
Products

Completely Stirred Tank Reactor

ACEE 219 Spring 2010 HDP 3

 CHAPTER 3.

CHEMICAL EQUIRIBRIUM

ACEE 219 Spring 2010 HDP 4

 Will this reaction go?
CaCO3 (s) + H+ → Ca2+ + HCO3-
when,
when
[CaCO3]=[H+]=[Ca2+]=[HCO3-]=1 mole/liter

“Will
Will this reaction go?”
go?

“How
How far can it proceed?”
proceed?

ACEE 219 Spring 2010 HDP 5

 Chemical Equilibrium
aA + bB ↔ cC + dD
on

on
A
oncentratio

oncentratio
C
B D
C A
Co

Co
D B
Time Time

• Chemical equilibrium: The state in which the chemical

concentrations (or activities) of the reactants and products have no
net change over time in a chemical reaction
reaction.

[C]ceq [D]deq
a b
=K
[A] [B]
eq eq K: Equilibrium constant
ACEE 219 Spring 2010 HDP 6
Chemical Equilibrium
Equilibrium, Cont
Cont’d
d
aA + bB ↔ cC + dD

[C]ceqq [D]deqq
a b
=K
[A] [B]
eq eq

• Small K:
N2(g) + O2(g) ↔ 2NO(g) K=10-30
- Forward reaction: reaction will be minimal.
- Reverse
R reaction:
ti reaction
ti will
ill almost
l t reach
h completely.
l t l

•Large K:
HCl ↔ H+ + Cl- K=103
- Forward reaction: reaction will almost reach completely.
- Reverse reaction: reaction will be minimal.

ACEE 219 Spring 2010 HDP 7

Chemical Equilibrium
Equilibrium, Cont
Cont’d
d
aA + bB ↔ cC + dD
[C]ceq [D]deq
a b
=K
[A] [B]
eq eq

• Factors affecting chemical equilibrium

- Addition (or removal) of reactants or products: we will discuss later.
- Volume change in a system: not so significant in aqueous reactions.
- Temperature: Van’t Hoff equation.

ACEE 219 Spring 2010 HDP 8

Chemical Equilibrium
Equilibrium, Cont
Cont’d
d
• Example (Calculation of equilibrium concentrations)
In a specified condition, nitrogen gas reacts with oxygen gas and
produces nitric oxide gas.
N2(g) + O2(g) ↔ 2NO(g) K=0.1
Initially, the concentrations of nitrogen, oxygen, and 0.1 M, 0.1M, and
0M respectively.
0M, ti l Calculate
C l l t concentrations
t ti off each
h species
i att
equilibrium condition.
Species Initial conc.
conc Delta conc.
conc Equ conc.
Equ. conc
N2 0.1 -x 0.1 – x
O2 0.1 -x 0.1 – x
NO 0 + 2x 2x

[NO]2eq (2x)2
K= = = 0.1 x=0.014 [ 2]]=[N
[O [ 2]]=0.086
[N2 ]eq [O 2 ]eq (0 1− x)(0.1
(0.1 x)(0 1− x)
[NO]=0.028
ACEE 219 Spring 2010 HDP 9
 Is Chem
Chem. Equilibrium Static?
• The interaction of reactants and p products does not cease when
equilibrium is reached. → DYNAMIC!!
• A chemical is at equilibrium if its forward rate of reaction (vf) is equal
to the rate of the reaction (vr).
)

aA + bB ↔ cC + dD

vf = k1[A]a[B]b
Assuming the reaction
is elementary
vr = k2[C]c[D]d

@ equilibrium (vf=vr),
) k1[A]a[B]b = k2[C]c[D]d

[C]c [D]d k 1
a b
= =K
[A] [B] k2
ACEE 219 Spring 2010 HDP 10
 Is it at equilibrium state?
CaCO3 (s) + H+ → Ca2+ + HCO3-
when,
when
[CaCO3]=[H+]=[Ca2+]=[HCO3-]=1 mole/liter

“Will
Will this reaction go?”
go?

“How
How far can it proceed?”
proceed?

ACEE 219 Spring 2010 HDP 11

 Free Energy

Part of the total energy that The total energy

is available to perform content of an element
useful work or compound

G = H – TS Partt off the

P th total
t t l energy
that is not available to
perform useful work
where,,
G: Gibbs free energy, kcal
T: absolute temperature, oK
S: entropy, kcal/oK
H: enthalpy, kcal

@ closed
l d system,
t constant
t t temperature
t t and
d pressure

ACEE 219 Spring 2010 HDP 12

 Total Free Energy (GT)
• The total free energy
gy ((GT) is the sum of the free energies
g of each of the reaction
components.

aA + bB ↔ cC + dD
The free energy per mole of D

GT = n A G A + nB GB + nC GC + nD GD
Th number
The b off moles
l off D
Only products
Only reactants C and D p
present
A and B present
GT

Minimum GT,
reaction at equilibrium
Extent of reaction
ACEE 219 Spring 2010 HDP 13
 Total Free Energy (GT)

GT,A
TA GT
GT,B

A B C Extent of reaction

ΔGT,
T A→B = GT,B
T B – GT,A
TA < 0 : The reaction can occur spontaneously.
p y

ΔGT,B→A = GT,A – GT,B > 0 : The reaction cannot occur spontaneously.

ΔGT,B→B
T B B = GT,B
T B – GT,B
TB = 0 : The reaction is at equilibrium.
equilibrium

Reactions proceed to a direction minimizing free energy of a system!!!

ACEE 219 Spring 2010 HDP 14

 ΔG
The change in GT is proportional to ∆G.

ΔG = (Σν i Gi )Product − (Σν i Gi )Reactants

i i

aA + bB ↔ cC + dD
c d
{C} {D}
ΔG = ΔGo + RTln
{A} a {B} b
where,

ΔGo: standard free energy (all of reactants and products are 1M and STP)
vi: stoichiometric coefficient of species i
{ }: activity, or active concentration (molar conc. in dilute solution)

The value of ∆G for a reaction provide us with a powerful tool to predict

whether or not reactions are possible.

ACEE 219 Spring 2010 HDP 15

 Calculation of ΔGo
Per mole

ΔG = (Σ v i G )
o o
i Products − (Σ v i G ) o At standard state
i Reactants
i i

ΔG o = (Σ v i ΔG f,oi ) Products − (Σ v i ΔG f,oi ) Reactants

i i

• Elements (e.g., O2, H2, C) = 0 kcal/mole

• H+, H2O = 1 mole/liter
• H+ = 0 kcal/mole
• {Gas} = partial pressure, atm
where,
vi: stoichiometric constant of species i
Gio : free energy per mole of species i at 1atm and 25oC
gy of formation p
ΔGf,f i : standard free energy per mole of species
p i
o

ACEE 219 Spring 2010 HDP 16

 Calculation of ΔGo
Calculate ΔGo for the transformation of CaCO3(s) to Ca2+ and HCO3-.

CaCO3(s) + H+ → Ca2+ + HCO3-

o
C
Compound
d ΔG (k
(kcal/mole)
f l/ l )
CaCO3(s) -269.78
H+ 0
Ca2+ -132.18
HCO3- -140.31

o
(
ΔG = Σ ν i ΔG
i
o
f,i )
Products
(
− Σ ν i ΔG
i
o
f,i )
Reactants

= (Δ G
o
f,Ca 2+
o
)( o
+ Δ G f,HCO3− − Δ G f,H + + Δ G f,CaCO3
o
)
= (-132.18
( 132 18 -140.31)
140 31) - (0 - 269.78)
269 78) = - 2.71
2 71 kcal The reaction is possible
(i.e., spontaneous).

ACEE 219 Spring 2010 HDP 17

 Calculation of K
• Wh a system
When t is
i att equilibrium
ilib i t t ΔG will
state, ill b
be zero. Reaction quotient
c d c d
{C} {D} [C] [D]
ΔG = ΔGo + RTln a b
≅ ΔG o
+ RTln a b
= ΔG o
+ RTlnQ
{A} {B} [A] [B]
In dilute solution where { } = [ ]

0 = ΔGo + RTlnK At equilibrium condition i) ∆G=0 and ii) Q=K

- ΔGo
lnK =
RT
- ΔGo
K = exp( )
RT

ACEE 219 Spring 2010 HDP 18

 Calculation of K
ΔG = ΔGo + RTlnQ
RTl Q
= - RTlnK + RTlnQ
Q
= RTln
K

• If Q/K >1, then ∆G is positive and the reaction is impossible as

written.

• If Q/K =1, then ∆G =0 and the reaction is at equilibrium.

• If Q/K <1, then ∆G is negative and the reaction is spontaneous as

written.

ACEE 219 Spring 2010 HDP 19

 Example 3
3--1
1 D
1. Determine
t i th
the equilibrium
ilib i constant
t t ffor th
the reaction
ti iin which
hi h liliquid
id
H2O dissociates to H+ and OH- at 25oC.

H2O ↔ H+ + OH-
o
Compound ΔG (kcal/mole)
f

H2O -56.69
H+ 0
OH- -37.60
37 60

(
ΔG o = Σ v i ΔG f,o,i
i
)
P d t
Products
(
− Σ v i ΔG f,o,i
i
)
R t t
Reactants
= (0 - 37.60) – (-56.69 ) = +19.09 kcal/mole

- ΔGo
K = exp( ) = exp(-19.09/[(1.99x10-3)x(298)] = 1.05x10-14 ≈ 1x10-14
RT
Kw
Snoeyink & Jenkins Example 3-1
ACEE 219 Spring 2010 HDP 20
 Example 3
3--1
1, Cont’d
Cont d
2 IIs this
2. thi reaction
ti proceeding
di as written
itt when
h [H+] = 10-66 M and
d [OH-]
= 5 x 10-8 M?

H2O ↔ H+ + OH-

+ - + -
{H }{OH } [H ][OH ]
ΔG = ΔG + RTln
o
≅ ΔG + RTln
o

{H2O} [H2O]
−6 −8
(10 ) × (5 × 10 )
ΔG = 19.09 + 1.99 × 10 −3 × 298 × ln
(1)
= +0.928
0.928 kcal/mole

The reaction as written is not possible

ACEE 219 Spring 2010 HDP 21

 Example 3
3--2
Fi d the
Find th equilibrium
ilib i constant
t t ffor th
the reaction
ti att 25oC,
C

2Fe2+ + 0.5O2 +5H2O↔ 2Fe(OH)3(s) + 4H+

o
Compound (kcal/mole)
ΔG f

Fe2+ -20
20.30
30
O2 0
H 2O -56.7
Fe(OH)3(s) -166 0
-166.0
H+ 0

(
ΔG o = Σ v i ΔG f,oi
i
)
P d t
Products
(
− Σ v i ΔG f,oi
i
)
R t t
Reactants
= [ 2(-166.0) +4(0)] – [2(-20.30)+ 0.5(0) + 5(-56.7)]
= -7.9 kcal/mole
- ΔGo
K = exp( ) = exp(7.9/[(1.99x10-3)x(298)] = 6.1x105
RT
Snoeyink & Jenkins Example 3-2
ACEE 219 Spring 2010 HDP 22
 Calculation of ΔHo
o o
ΔH = (Σ ν i H )
o
f,i Products − (Σ ν i H )
f,i Reactants
i i

• Elements (e.g., O2, H2, C) = 0 kcal/mole

• H+, H2O = 1 mole/liter
• H+ = 0 kcal/mole
• {Gas} = partial pressure, atm

where,
vi: stoichiometric constant of species i
o
ΔHf,i : standard enthalpy of formation per mole of species i

• ∆H < 0 : Heat is evolved and the reaction is called exothermic

• ∆H > 0 : Heat is taken up and the reaction is called endothermic

ACEE 219 Spring 2010 HDP 23

Effect of Temp.
Temp on K
Van’t Hoff Equation

d lnK ΔHo
=
dT RT 2
K2 ΔHo T2 dT
∫K1
l K=
d lnK
R ∫T1 T2

T
ΔHo ⎡ 1⎤
2

[lnK ]KK 2
= ⎢− T ⎥
1
R ⎣ ⎦ T1

K1
K 1 ΔHo 1 1 K2 =
ln = ( − ) or ⎡ ΔHo 1 1 ⎤
K2 R T2 T1 exp
p⎢ ( − )⎥
⎣ R T2 T1 ⎦
ACEE 219 Spring 2010 HDP 24
 Effect of Temp.
Temp on K
K 1 ΔHo 1 1
ln = ( − )
K2 R T2 T1

• If reaction ∆H is negative (i.e., exothermic), increasing temperature

cause decrease in K.

• If reaction ∆H is positive (i.e., endothermic), increasing temperature

cause increase in K.

ACEE 219 Spring 2010 HDP 25

 Example 3
3--4
Q: What will be the condition of water saturated with respect to
CaCO3(s) at 25oC as the water is at 60oC and 15oC, respectively?
(ΔGo = -2.71 kcal/mole)

CaCO3(s) + H+ ↔ HCO3- + Ca2+

- ΔGo
1. K = exp( ) = exp(2.71/[(1.99x10
exp(2 71/[(1 99x10-3)x(298)] = 96
96.5
5
RT
2. ΔHo = (Σ v i ΔHof,i )Product − (Σ v i ΔHof,i )Reactants = -129.77 – 165.18 - (-288.45) - (0)
i i
= -6.5
6 5 kcal

Compound ΔHof (kcal/mole)

CaCO3(s) -288.45
H+ 0
HCO3- -129.77
Ca2+ -165.18

ACEE 219 Spring 2010 HDP 26

 Example 3
3--4
3. At 60oC
K1
K2 = = 96.5
⎡ ΔH 1 1 ⎤
o
⎡ − 6.5 ⎛ 1 1 ⎞⎤
expp ⎢ ( − )⎥ p⎢
exp −3 ⎜ − ⎟⎥
⎣ R T2 T1 ⎦ ⎣1 .99 × 10 ⎝ 333 298 ⎠⎦

= 30.49 > 96.5 Oversaturated with

respective to CaCO3(s)!!

4. At 15oC
K1
K2 = = 96.5
⎡ ΔH 1 1 ⎤
o
⎡ − 6.5 ⎛ 1 1 ⎞⎤
exp ⎢ ( − )⎥ exp ⎢ −3 ⎜
− ⎟⎥
⎣ R T2 T1 ⎦ ⎣1. 99 × 10 ⎝ 288 298 ⎠⎦

= 141.2 < 96.5 Undersaturated with

respective to CaCO3(s)!!
ACEE 219 Spring 2010 HDP 27
 Activity
• Activity: A measure of effective concentration in a mixture.
mixture In a
dilute solution activities are similar to the molar concentrations (i.e.,
activity coefficient ≈ 1.0),

{i} = γi[i]
where, {i} is activity of species i, γi is activity constant, and [i] is
molar concentration of species i in a solution.

• DeBye-Huckel limiting law: A relationship between activity

coefficient and ionic strength for ions in a solution,

log γi =0.5Z
-log 0.5Zi2μ1/2
where, Zi is charge of species i and μ is ionic strength of species in
a solution.

ACEE 219 Spring 2010 HDP 28

 Is it at equilibrium state?
CaCO3 (s) + H+ → Ca2+ + HCO3-
when,
when
[CaCO3]=[H+]=[Ca2+]=[HCO3-]=1 mole/liter

“Will
Will this reaction go?”
go?

“How
How far can it proceed?”
proceed?

ACEE 219 Spring 2010 HDP 29

 Lecture for the Next Week

1. Introduction of acid-base chemistry

2 Equilibrium calculation (computational approach)
2.
- Mass balances
- Equilibrium
E ilib i relationships
l ti hi
- Proton condition
- Charge balance
3. Strong acid and strong base
4. Weak acid and weak base

ACEE 219 Spring 2010 HDP 30