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CE4501 Environmental Engineering Chemical Processes

Problem Set 1 - SOLUTIONS


Fall 2008

1 . Problem 2.7 in the text (p. 31)


Calculate the molarity and normality of the following solutions:
a) 20 g/L NaOH
MW = 1x23 + 1x16 + 1x1 = 40
g mole
mole
Molarity = 20
= 0.5
L 40 g
L
mole
eq
eq
Normality = 0.5
1
= 0.5 = 0.5 N
L
mole
L

b) 25 g/L H2SO4
MW = 2x1 + 1x32 + 4x16 = 98 g/mole
g mole
mol
Molarity = 25
= 0.255
= 0.255M
L 98 g
L
mole
eq
eq
Normality = 0.255
2
= 0.51 = 0.51N
L
mole
L
------------------------------------------------------------------------------2. Problem 2.8 in the text (p. 31)
The major ions in a groundwater sample are:
[Ca2+] = 75 mg/L
[Mg2+] = 40 mg/L
[Na+] = 10 mg/L
[HCO3-] = 300 mg/L
[Cl-] = 10 mg/L
[SO42-] = 109 mg/L
a) Calculate the concentration of each ion in molarity and normality on a charge basis.
mg mmol
Molarity = 75

= 1.875mM
L 40mg
Ca
mmol
meq
meq
Normality = 1.875
2
= 3.75
L
mmol
L
mg mmol
Molarity = 40

= 1.646mM
L 24.3mg
Mg
mmol
meq
meq
Normality = 1.646
2
= 3.292
L
mmol
L
mg mmol
Molarity = 10

= 0.435mM
L 23mg
Na
mmol meq
meq
Normality = 0.435
1
= 0.435
L
mmol
L

mg mmol

= 4.918mM
L 61mg
mmol meq
meq
Normality = 4.918
1
= 4.918
L
mmol
L
mg mmol
Molarity = 10

= 0.282mM
L 35.5mg
mmol meq
meq
Normality = 0.282
1
= 0.282
L
mmol
L
mg mmol
Molarity = 109

= 1.135mM
L 96mg
mmol
meq
meq
Normality = 1.135
2
= 2.27
L
mmol
L

Molarity = 300
HCO3-

Cl

SO42-

b) Is the ground water electrically neutral


Cations: 3.75 + 3.292 + 0.435 = 7.477 meq/L
Anions: 4.918 + 0.282 + 2.27 = 7.470 meq/L
Because the concentration of cationic charges equals the sum of anionic charges, the sample is
electrically neutral.
c) Calculate the TDS of the water.
TDS = 75 + 40 + 10 + 300 + 10 + 109 = 544 mg/L
-----------------------------------------------------------------------------------3. Problem 2.10 in the text (p. 31)
a) Calculate the hardness of a water containing 80 mg/L of Ca2+.
mgCaCO3
mgCa 2+ mmole mmoleCaCO3
mg

1
100
= 200
as CaCO3
Hardness = 80
2+
40mg
L
mmoleCa
mmole
L
b) Calculate the hardness of the ground water in the previous problem.
Ca Hardness = 75

mgCa 2+ mmole mmoleCaCO3


mgCaCO3
mg

1
100
= 188
as CaCO3
2+
L
mmoleCa
mmole
L
40mg

mgCa 2+ mmole mmoleCaCO3


mgCaCO3
mg
as CaCO3

1
100
= 165
2+
L
24.3mg
mmoleMg
mmole
L
mg
Total hardness = 188 + 165 = 353
as CaCO3
L
Mg Hardness = 40

c) How much calcium ion would be required to account for a hardness of 150 mg/L as CaCO3?
mgCaCO3 mmolCaCO3
mmol Ca 2+
mg
mgCa 2+

1
40
= 60
150
L
100mg
mmol CaCO3
mmol Ca 2+
L

4. Problem 3.5 in the text (p. 64). Ignore activity corrections.


Consider the reaction:
NH4+ NH3 + H+
a. Is the reaction endothermic or exothermic if all concentrations are 0.01 M?
SOLUTION:
Whether a reaction is exo- or endothermic depends on the enthalpy, H, of reaction.
Under standard conditions, H 0 = i H 0f ,i i H 0f ,i
products

reactants

Thus,

moleNH 3
mole H +
mole NH 4+

0
0
0
H = 1
H f , H + 1
H f , NH 4+
H f , NH3 + 1
mole of reaction
mole of reaction
mole of reaction


moleNH 3
kJ
kJ
mole H +

H 0 = 1

+
80.3
1

0

+
mole NH 3 mole of reaction mole H
mole of reaction
0

mole NH 4+
kJ
1
132.5
+
mole NH 4
mole of reaction
kJ
H 0 = +52.2
mole of reaction
Under standard conditions (1 atm, 25oC, 1 M conc. of all species) the reaction is endothermic
because the heat content of the products is greater than that of the reactants.
b. Would the reaction proceed spontaneously if the concentrations of all species were 0.01
(assume T = 25oC, P = 1 atm)?
SOLUTION:
The problem asks if G is negative for the reaction under the stated conditions; if G is
negative, the reaction can proceed spontaneously. Recall,
G = G 0 + RT ln(Q)
G 0 =

i G 0f ,i

products

Q=

i G 0f ,i

products

{ NH 3}{H + }

{ NH }
+
4

Using these relationships, we can find G:

G = G 0 + RT ln(Q)
G 0 =

i G 0f ,i

G = 1 G

i G 0f ,i

products

products
0

0
f , NH 3

+ 1 G 0f , H + 1 G 0f , NH +
4

kJ
kJ
kJ

kJ

G 0 = 1 26.57
+ 1 0
1 79.37
= +52.8
mole
mole
mole

mole

{ NH 3}{H + } {0.01}{0.01}
Q=
=
= 0.01
{0.01}
{ NH 4+ }

J
kJ
kJ

3 kJ
+ 8.314
( 298K ) 10
ln ( 0.01) = +41.39
mole
mole K
J
mole

Because G is positive, the reaction cannot proceed spontaneously as written when all
concentrations are equal to 0.01M.
G = +52.8

5. Problem 3.7 in the text (p. 64). Ignore activity corrections.


Calculate K for the reaction: NH4+ NH3 + H+
SOLUTION
G 0
Recall that K = exp

RT
In the previous problem we found Go to be +52.8kJ/mole.
kJ

52.8

10
mole
Therefore, K = exp
= 5.55 x10
kJ
3
8.314 x10
298 K
mole K

+
{ NH 3}{H }
We can use the expression K =
to find that the pH at which the ratio of
{NH 4+ }

{NH3}/{NH4+} equals 1 is pH = -log(K) = 9.26. At lower pH, the concentration of NH4+ will
exceed the concentration of NH3.
6. Problem 4.6 in the text (p. 85).
Write the balanced equation for the conversion of Al(OH)2+ to Al(OH)2+
SOLUTION:
Al(OH)2+ + H2O Al(OH)2+ + H+
7. Problem 4.8 in the text (p. 86). Ignore activity corrections.
What is the equilibrium constant for the reaction equation from the previous problem?
SOLUTION

We first arrange the component reactions such that when added they yield the equation in
problem 6.
Al(OH)2+ + 2OH- AL(OH)3(s)
AL(OH)3(s) + 3H+ Al3+ + 3H2O
Al3+ + 2OH- Al(OH)2+
4(H2O H+ + OH-)
Al(OH)2+ + H2O Al(OH)2+ + H+

K = 1022.2
K = 1010.8
K = 1018.5
K = (10-14)4 = 10-56
K = 10-4.5

8. Calculate the ionic strength of the following solutions and calculate the activity coefficient
(using the Davies equation) for the ion in parentheses.
a. 2.1 x 10-3 M NaNO3 (Na+)
SOLUTION:
Ionic strength
1
2

2
I = Ci zi2 = 0.5 Na + z Na
+ + NO3 z

NO3
2 i

I = 0.5 ( 2.1x103 12 + 2.1x103 12 ) = 2.1x103 M

Activity coefficient

I
log Na + = Az 2
0.2 I
1+ I

( 0.0021)0.5

2
log Na + = ( 0.5 )( +1)
0.2 0.0021
0.5
1 + ( 0.0021)

log Na + = 0.01981

Na = 0.955
+

-----------------------------------b. 2.8 x 10-4 M CaSO4 (Ca2+)


SOLUTION:
Ionic strength
1
2
2
2
I = Ci zi2 = 0.5 Ca 2+ zCa
2+ + SO4 z

SO42
2 i

I = 0.5 ( 2.8 x104 (+2) 2 + 2.2 x104 (2) 2 ) = 1.12 x103 M

Activity coefficient

I
0.2 I
log Ca2+ = Az 2
1+ I

log Ca2+

( 0.00112 )0.5

= ( 0.5 )( +2 )

0.2
0.00112

1 + ( 0.00112 )0.5

log Ca2+ = 0.0603

Ca = 0.871
2+

9.Giventheinformationbelowforthereactionshowncalculate:

a.GoR

b.K(equilibriumconstant)at25oC

c.Kat6oC

d.Gat25oC,anionicstrengthof5mMandthefollowingconcentrations:

CH3COO107M,SO4250M,HCO32mM,HS107M,pH7.0

Reaction:
CH3COO+SO42+H+
2HCO3+HS+2H2O(l)

Species

Gof(kcal/mol)
Hof

CH3COO

89.0

116.84
2

SO4

177.34

216.90

H+

HCO3

140.31

165.18

HS

+3.01

4.22

H2O(l)

56.69

68.317

SOLUTION
Theequationthatyouweregivenforthereactionincorrectlyindicatedthat2moleculesof
acetateareinvolvedinthereaction.Thecorrectequationisgivenabove.Thesolutionbelowis
shownforthecorrectreactionequation;valuesfortheincorrectequationaregivenin
parentheses.
0
Grxn
= i G 0f ,i i G 0f ,i
reactants

products

= 2 G

= 2 ( 140.31) + 1( 3.01) + 2 ( 56.69 ) 1( 89.0 ) 1( 177.34 ) 1( 0 )

0
rxn

A:

0
rxn

0
f , HCO3

0
Grxn
= 124.65

+ 1 G 0f , HS + 2 G 0f , H 2O 1 G 0f ,CH COO 1 G 0f , SO2 1 G 0f , H +

kcal
kcal
Rxn as given: -35.65

mol
mol

0
Grxn

K = exp

RT
kcal

124.65

mol

= exp ( 210.5 )
B: K = exp
1.987 x103 kcal 298 K

mol K

K = 2.6 x1091

( Rxn as given:

1.4x1026 )

K H 0 1 1
ln 2 =

R T1 T2
K1
H 0 =

i H 0f ,i

i H 0f ,i

reactants

products

H = 2 ( 165.18 ) + 1( 4.22 ) + 2 ( 68.317 ) 1( 116.84 ) 1( 216.9 ) 1( 0 )


0

kcal
kcal
Rxn as given: -20.63

mole
mol
kcal
137.5
1
1

mol

ln ( K 2 ) = ln ( 2.6 x1091 ) +

kcal 298.15K 273.15K + 6 K


1.982 x103
mol K
ln ( K 2 ) = 365

C: H 0 = 137.5

K 2 = 3.4 x10158

( Rxn as given:

1.5x1027 )

D.Wemustfirstfindtheactivitycoefficientsforionsofcharge1and2.

I
log ( ) = Az 2
0.2 I
1+ I

( 0.005 )0.5

2
log ( 1 ) = ( 0.5 )(1)
0.2
0.005

1 + ( 0.005 )0.5

log ( 1 ) = 0.02802

1 = 0.938

( 0.005 )0.5

log ( 2 ) = ( 0.5 )( 2 )
0.2
0.005

1 + ( 0.005 )0.5

log ( 2 ) = 0.11208
2

2 = 0.772
NowwecansolveforQ:

12 HCO3 1 HS 02 [ H 2O ]
Q= 1
1 [CH 3COO ] 2 SO42 1 H +
2

( 0.938) ( 2 x103 ) ( 0.938 ) (107 ) (1) (1)


Q=
( 0.938) (107 ) ( 0.772 ) ( 5 x105 )(107 )
2

Q = 9.12 x105

( Rxn as given:

9.72x1012 )

KnowingQ,wecansolveforG:
G = G 0 + RT ln(Q)

G = 124.65

kcal
kcal
5
+ 1.982 x103
( 298 K ) ln ( 9.12 x10 )
mol
mol K

kcal
kcal
Rxn as given: -17.98

mol
mol
BecauseGisnegative,thereactioncanproceedtotherightunderthestatedconditions.

G = 116.5

10.Thereactionshowninproblem3aboveisthesourceofenergyforsulfatereducing
bacteria.Thesebacteriaarecommoninlakesedimentsandsoils,especiallywhenoxygenisnot
present.Sulfatereducingbacteriamustcompetefortheirfood(CH3COO)withotherbacteria
suchasthosethatuseoxygenratherthansulfate.Undertypicalenvironmentalconditions
([O2(aq)]=2mg/L,PCO2=103.5atm)Gforthereactionbelowis199.8kcal/mole.

CH3COO+H++2O2(aq)<==>2CO2(aq)+2H2O(l)

Onthebasisofthermodynamics,whichbacterialgroupwouldyoupredicttohavethe
competitiveadvantageifbothoxygenandsulfatearepresentattheconcentrationsstated
above?Why?Howcouldthecompetitiveadvantageofsulfatereducingbacteriabeincreased?

SOLUTION:
The free energy yield for the aerobic bacteria (-199.8kcal/mole CH3COO-) is larger than that for
the sulfate reducing bacteria (-116.5 kcal/mole as calculated here or -17.98 kcal/mole as you
should have calculated) by a factor of 1.7 (11.1 from your calculations). Therefore, the aerobic
bacteria should be at a competitive advantage and should be able to outcompete the sulfate
reducing bacteria because they are gleaning more energy that can be used for biomass production
or other functions. As the concentration of oxygen decreases (e.g., in the sediments), the
competitive advantage of the aerobic bacteria will decrease. Lowering pH or increasing sulfate
concentration also would enhance the competitiveness of the sulfate reducing bacteria.