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Chapter 15:
Chemical Equilibrium
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Dynamic Equilibrium
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N2O4
2 NO2
Initially forward reaction rapid
As NO2 forms
Reverse rate
Ions collide more frequently as [ions]
Dynamic Equilibrium
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(Fig. 15.1)
Reaction Reversibility
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Closed system
Equilibrium can be
reached from either
direction
Independent of whether
it starts with reactants
or products
Always have the same
composition at
equilibrium under same
conditions
Jespersen/Brady/Hyslop
N2O4
2 NO2
5
Equilibrium
Products
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Reactants
N2O4
2 NO2
Equilibrium
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Forward reaction: A B
k
Reverse reaction: A B
A
B
At equilibrium:
kf
Rate = kf[A]
Rate = kr[B]
kf[A] = kr[B]
rearranging:
Jespersen/Brady/Hyslop
[ B] k f
= =constant
[ A] kr
Chemistry: The Molecular Nature of Matter, 6E
2HI(g)
440C
Equilm
Amts
0.222 mol H2
Equilm
[M]
0.0222 M H2
10 L 1.00 mol I2
0.222 mol I2
0.0222 M I2
0.00 mol HI
1.56 mol HI
0.156 M HI
0.00 mol H2
0.350 mol H2
0.0350 M H2
10 L 0.100 mol I2
0.450 mol I2
0.0450 M I2
3.50 mol HI
2.80 mol HI
0.280 M HI
II
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Expt
Initial
Amts
#
I 1.00 mol H2
Jespersen/Brady/Hyslop
440C
Equilm
Amts
Equilm
[M]
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2HI(g)
III
0.0150 mol H2
0.150 mol H2
0.0150 M H2
10 L
0.00 mol I2
0.135 mol I2
0.0135 M I2
1.27 mol HI
1.00 mol HI
0.100 M HI
IV
0.00 mol H2
0.442 mol H2
0.0442 M H2
10 L
0.00 mol I2
0.442 mol I2
0.0442 M I2
4.00 mol HI
3.11 mol HI
0.311 M HI
Jespersen/Brady/Hyslop
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[C ] c [ D ] d
Q=
[ A ] a [ B ]b
Reaction quotient
10
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[ HI ]
Q=
[ H 2 ][ I 2 ]
Equilibrium Concentrations
(M)
Expt
[H2]
[I2]
[HI]
0.0222
0.0222
0.156
II
0.0350
0.0450
0.280
III
0.0150
0.0135
0.100
IV
0.0442
0.0442
0.311
[ HI ]
Q=
[ H 2 ][ I 2 ]
2
(0 . 156)
=49. 4
(0 . 0222)(0 . 0222)
2
(0 . 280 )
=49 .8
(0 . 0350)(0 . 0450 )
(0 . 100)2
=49. 4
(0 . 0150)(0 . 0135)
2
(0 . 311)
=49. 5
(0 . 0442)(0 . 0442)
Average = 49.5
Jespersen/Brady/Hyslop
11
Equilibrium Law
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[ HI ]
K c=
=49. 5
[ H 2 ][ I 2 ]
12
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[ F ] [G ]
d
e
[D] [E ]
[ D] [ E]
Jespersen/Brady/Hyslop
13
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[ products ]
K c=
d
[ reactants ]
Jespersen/Brady/Hyslop
is scientists convention
14
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3 H2(g) + N2(g)
Kc = 4.26 x 108 at 25 C
What is equilibrium law?
K c=
[ NH3 ]
3
[ H 2] [ N 2]
Jespersen/Brady/Hyslop
=4 . 2610
15
Learning Check
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[ N 2O 4 ]
Q=
2
[ NO 2 ]
2CO (g) + O2 (g)
2 CO2 (g)
[CO 2 ]
Q=
2
[CO ] [O 2 ]
Jespersen/Brady/Hyslop
16
Your Turn!
A.
B.
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[Cu 2+ ][ NH 3 ]4
[ Cu ][ NH3 ]
2+
[ Cu ][ NH 3 ]
C. Q =
2+
[ Cu( NH 3 )4 ]
D . none of these
Jespersen/Brady/Hyslop
17
A+B
C +D
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A+B
Jespersen/Brady/Hyslop
[ C ][ D ]
K c=
[ A][ B ]
[ A][ B ] 1
K c=
=
[ C ][ D ] K c
'
18
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3 H2(g) + N2(g)
K c=
[ NH3 ]
3
2 NH3(g)
at 25C
[ H 2] [ N 2]
=4 . 2610
2 NH3(g)
3 H2(g) + N2(g)
at 25C
3
[ H 2] [ N 2] 1
1
'
9
K c=
= =
=2 . 3510
2
8
K c 4 . 2610
[ NH3 ]
Jespersen/Brady/Hyslop
19
Manipulating Equilibria 2
A+B
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[ C ][ D ]
K c=
[ A][ B ]
C+D
3A + 3B
3
3C + 3D
[C ] [ D ] [C ][ D ] [ C ][ D ] [C ][ D ] 3
Kc= 3 3 =
=K c
[ A ] [ B ] [ A ][ B ] [ A][ B ] [ A][ B ]
''
Jespersen/Brady/Hyslop
20
Manipulating Equilibria 2
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K c=
[ NH3 ]
[ H 2] [ N 2]
=4 . 2610
multiply by 3
9 H2(g) + 3 N2(g) 6 NH3(g)
6
[ NH 3 ]
''
Kc=
3
=K c
3
[ H 2 ]9 [ N 2 ]
Jespersen/Brady/Hyslop
21
Manipulating Equilibria 3
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C+E
F+G
A+B+E
[ A][ B ]
[ F ][G ]
Kc =
2
[C ][ E ]
D+F+G
[ C ][ D ] [ F ][G ] [ D ][ F ][ G ]
Kc =
=
=K c K c
1
2
3
[ A][ B ] [C ][ E ] [ A ][ B ][ E ]
Jespersen/Brady/Hyslop
22
Manipulating Equilibria 3
2 NO2(g)
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NO3(g) + CO(g)
NO2(g) + CO2(g)
NO2(g) + CO(g)
NO(g) + CO2(g)
Kc =
[ NO ][ NO3 ]
2
[ NO 2 ]
[ NO2 ][ CO 2 ]
Kc =
2
[ NO3 ][ CO ]
1
[ NO ][ CO 2 ]
Kc =
3
[ NO2 ][ CO ]
[ NO ][ CO 2 ]
[ NO ][ NO 3 ] [ NO2 ][CO 2 ]
=
[ NO2 ][ CO ]
[ NO 3 ][ CO ]
[ NO 2 ] 2
K c K c =K c
Therefore
1
Jespersen/Brady/Hyslop
23
Learning Check
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N2(g) + 3 H2(g)
1
1
'
K c=
=
= 0.002
K c 500
K c =K
1/ 2=
Jespersen/Brady/Hyslop
NH3(g)
500= 22.4
24
Equilibrium Constant, Kc
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[ products ]
K c=
d
[ reactants ]
25
Equilibrium Constant, Kp
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K P=
P NH 3
PN P
2
Jespersen/Brady/Hyslop
3
H
26
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()
K p =K c ( RT )
Jespersen/Brady/Hyslop
27
Learning Check
N2O4(g)
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K p=K c (RT)
Kp
0 . 480
K c=
=
n
1
(RT)
(0 . 0821298 K )
Kc = 11.7
Jespersen/Brady/Hyslop
28
Your Turn!
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Jespersen/Brady/Hyslop
n=(4 3)=1
Kp = Kc(RT)n
Kp= 0.99*(0.082057*298.15)1
Kp = 24
29
Homogeneous reaction/equilibrium
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Heterogeneous reaction/equilibrium
Jespersen/Brady/Hyslop
30
Heterogeneous Equilibria
Na2CO3(s) + H2O(g) + CO2(g)
[ Na2 CO 3 ( s ) ][ H 2 O ( g ) ][CO 2 ( g ) ]
Equilibrium Law =
K=
[ NaHCO 3 ( s) ] 2
Can write in simpler form
For any pure liquid or solid, ratio of moles to
volume of substance (M) is constant
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2NaHCO3(s)
M=
2 mol NaHCO3
0 . 0778 L
=25. 7M
1 mol NaHCO 3
=25 . 7M
0. 0389
L
Jespersen/Brady/Hyslop
31
Heterogeneous Equilibria
2NaHCO3(s)
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32
Learning Check
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H3PO4(aq) + H2O()
] [ Cl
H3O+(aq) + H2PO4(aq)
+
[ H 3 O ][ H 2 PO ]
K c=
[ H 3 PO 4 ]
Jespersen/Brady/Hyslop
33
Your Turn!
Ca3(PO4)2(s)
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Q=
2
[Ca 2+ ]3 [ PO3
]
4
[Ca 3 ( PO 4 )2 ]
Q=
2
[Ca 2+ ]3 [PO 3
]
4
[1 ]
[ Ca 3 (PO4 )2 ]
Q = 2+ 3
2
[ Ca ] [ PO 3
]
4
[1 ]
Q = 2+ 3
3 2
[Ca ] [ PO 4 ]
Jespersen/Brady/Hyslop
34
Your Turn!
Ca3(PO4)2(s)
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Q=
[Ca 3 ( PO 4 )2 ]
2+ 3
B.
C.
D.
Jespersen/Brady/Hyslop
Q=
[Ca ]
3 2
[PO 4 ]
[1 ]
[ Ca 3 (PO 4 )2 ]
Q = 2+ 3
2
[ Ca ] [ PO3
]
4
[1 ]
Q= 2+ 3
3 2
[Ca ] [ PO4 ]
35
Interpreting KC
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Large K (K>>1)
2SO3(g)
Kc = 7.0 1025 at 25 C
[ SO 3 ]
7 . 010
K c=
=
2
1
[ SO 2 ] [O 2 ]
Jespersen/Brady/Hyslop
25
36
Interpreting KC
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Small K (K<<1)
Means reactant rich
mixture
Only very small amounts of
product formed
Ex.
H2(g) + Br2(g)
2HBr(g)
Kc = 1.4 1021 at 25 C
Jespersen/Brady/Hyslop
21
[ HBr ]
1 . 410
K c=
=
[ H 2 ][ Br 2 ]
1
Chemistry: The Molecular Nature of Matter, 6E
37
K 1
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Interpreting KC
Means product and
reactant concentrations
close to equal
Reaction goes only ~
halfway
Jespersen/Brady/Hyslop
38
K >> 1
K=1
K << 1
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Jespersen/Brady/Hyslop
39
Learning Check
N2O4(g)
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K is small (K < 1)
Reaction favors reactant
Since K is close to 1, significant amounts of
both reactant and product are present
Jespersen/Brady/Hyslop
40
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Equilibrium positions
Combination of concentrations that allow Q = K
Infinite number of possible equilibrium positions
Le Chteliers principle
41
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Q=K
Q<K
Q>K
reactants products
42
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Jespersen/Brady/Hyslop
43
yellow
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blue
CuCl42(aq) + 4H2O
4
[ Cu( H 2 O )2+
(
aq
)
][
Cl
(
aq
)
]
4
'
K c=
Kc
[ H 2O ]
[ CuCl4
( aq) ]
4
[ Cu( H 2 O )2+
(
aq
)
][Cl
(
aq
)
]
4
44
yellow
2
[ CuCl 4 ( aq ) ]
K c=
4
[ Cu( H 2 O )2+
(
aq
)
][
Cl
(
aq
)
]
4
Add Ag+
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blue
CuCl42(aq) + 4H2O
Removes Cl:
Ag+(aq) + Cl(aq) AgCl(s)
Equilibrium shifts to reactants
Makes more blue Cu(H2O)42+
Solution becomes bluer
Add H2O?
Jespersen/Brady/Hyslop
45
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Jespersen/Brady/Hyslop
46
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Jespersen/Brady/Hyslop
47
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P N PH
2
Expect Pressure to increase (P)
To reduce pressure, look at each side of reaction
Which has less moles of gas
Reactants = 3 + 1 = 4 moles gas
Products = 2 moles gas
Reaction favors products (shifts to right)
Jespersen/Brady/Hyslop
48
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49
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2NaHSO3(s)
K P =P H
P
O SO
50
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51
Ice
water
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Cu(H2O)42+(aq) + 4Cl(aq)
blue
Boiling
water
CuCl42(aq) + 4H2O
yellow
Reaction endothermic
Adding heat shifts equilibrium toward products
Cooling shifts equilibrium toward reactants
Jespersen/Brady/Hyslop
52
H =+6 kJ (at 0 C)
H2O()
H2O()
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Energy + H2O(s)
Energy is reactant
Add heat, shift reaction right
3H2(g) + N2(g)
3 H2(g) + N2(g)
Energy is product
Add heat, shift reaction left
Jespersen/Brady/Hyslop
53
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54
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Catalyst lowers Ea
for both forward
and reverse
reaction
Change in Ea
affects rates kr
and kf equally
Catalysts have no
effect on
equilibrium
Jespersen/Brady/Hyslop
55
Inert gas
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56
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Jespersen/Brady/Hyslop
57
Learning Check:
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Consider:
H3PO4(aq) + 3OH(aq)
3H2O() + PO43(aq)
3
[ PO 4 ]
Q=
3
[OH ] [ H 3 PO 4 ]
58
Learning Check:
3H2O(aq) + PO43(aq)
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The reaction
H3PO4(aq) + 3OH(aq)
heat
is exothermic.
What will happen if system is cooled?
3
[ PO 4 ]
Q=
3
[OH ] [ H 3 PO 4 ]
59
Your Turn!
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[Co(Cl)4]2(aq) + 6H2O()
blue
60
Your Turn!
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C. Ka = 4.01010
D. Ka = 6.3103
Jespersen/Brady/Hyslop
61
Equilibrium Calculations
For gaseous reactions, use either KP or KC
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Jespersen/Brady/Hyslop
62
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63
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Ex. 1 N2O4(g)
[NO2]eq = 0.0116 M
2
2
[ NO 2 ]
[ 0 . 0116 ]
K c=
K c=
[ N 2O4]
[ 0 . 0292]
KC = 4.61 103
Jespersen/Brady/Hyslop
64
Your Turn!
A. 14
B. 0.15
C. 1.5
D. 6.75
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[C ]
K c= 2
[ A] [ B]
[ 3. 0 ]
K c=
2
[ 2 . 0 ] [1 . 0 ]
Jespersen/Brady/Hyslop
65
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1 .00 mol
[ SO 2 ]=[O 2 ]=
=1 .00 M
1. 00 L
Equilibrium
0 .925 mol
[ SO 3 ]=
=0 . 925 M
1 . 00 L
Jespersen/Brady/Hyslop
66
How to Solve:
Set up Concentration Table
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Initial concentrations
Changes in concentrations
Equilibrium concentrations
Equilibrium
=
Concentration
Change in
Initial
Concentration
Concentratio
nChemistry: The Molecular Nature of Matter, 6E
Jespersen/Brady/Hyslop
67
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2SO2(g) + O2(g)
1.000
0.462
0.538
2SO3(g)
0.000
+0.925
0.925
68
Ex. 2
K c=
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[SO 3 ]
[ SO 2 ] [O 2 ]
[ 0. 925 ]
K c=
2
[ 0 . 075] [0 . 538 ]
Jespersen/Brady/Hyslop
69
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70
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71
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72
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[ CO ][ H 2 ]
[ H 2 O ]=
[ CH 4 ][ H 2 O ]
[ CO][ H 2 ]
[CH 4 ] K c
73
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Jespersen/Brady/Hyslop
74
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KC = 55.64
[ HI ]
K c=
=55 . 64
[ H 2 ][ I 2 ]
Jespersen/Brady/Hyslop
75
H2(g) +
I2(g)
2HI (g)
2.00
x
2.00 x
0.000
+2x
+2x
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Conc (M)
2.00
x
2.00 x
( 2x )
( 2x )
55 .64=
=
(2 . 00 x )(2 . 00 x ) (2 .00x )2
Jespersen/Brady/Hyslop
76
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(2x )
K= 55 . 64=
2
(2 . 00 x )
2x
7 . 459=
(2. 00x )
7 . 459(2 . 00 x )=2x
14 .918=9. 459 x
14 . 918
x=
=1 . 58
9. 459
Jespersen/Brady/Hyslop
77
Initial
Change
Equilm
H2(g) +
I2(g)
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Conc (M)
2.00
1.58
0.42
2.00
1.58
0.42
2HI (g)
0.00
+3.16
+3.16
Jespersen/Brady/Hyslop
78
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KC = 55.64
[ HI ]
K c=
=55 . 64
[ H 2 ][ I 2 ]
Jespersen/Brady/Hyslop
79
H2(g) +
I2(g)
2HI (g)
2.00
x
2.00 x
2.00
+2x
2.00 + 2x
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Conc (M)
2.00
x
2.00 x
(2 .00 +2x )2
(2 .00 +2x)2
55 .64=
=
(2 . 00 x )(2 . 00 x ) ( 2. 00x ) 2
(2 . 00+2x )
K= 55 . 64=
2
(2. 00x )
Jespersen/Brady/Hyslop
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2 . 00+2x
7 . 459=
(2. 00x )
12 . 918
x=
=1 . 37
9. 459
Jespersen/Brady/Hyslop
81
Your Turn!
N2(g) + O2(g)
2NO(g)
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Kc = 0.0123 at 3900 oC
82
N2(g) +O2(g)
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2NO (g)
1.00
1.00
0.00
x
x
+ 2x
1.00 x 1.00 x
+ 2x
0.250 mol
[N2 ] = [O2 ] =
= 1.00M
0.250 L
(2x )2
2x
0.0123 =
0.0123 =
2
1 x
(1 x )
x = 0.0526M [NO] = 2x = 0.105M
Jespersen/Brady/Hyslop
83
Ex. 6
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ethanol
CH3CO2C2H5(aq) +
ethyl acetate H2O(l)
KC = 0.11
An aqueous solution of ethanol and acetic
acid, each with initial concentration of 0.810
M, is heated at 100 C. What are the
concentrations of acetic acid, ethanol and
ethyl acetate at equilibrium?
Jespersen/Brady/Hyslop
84
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K c=
[ CH 3 CO 2 C 2 H 5 ]
[ C 2 H 5 OH ][CH 3 CO 2 H ]
85
0.810
C2H5OH(aq)
0.810
CH3CO2C2H5(aq) + H2O(l)
0.000
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(M) CH3CO2H(aq) +
x
0.810 x
x
0.810 x
+x
+x
Jespersen/Brady/Hyslop
x
0 .11=
(0 .810x )(0. 810x )
Chemistry: The Molecular Nature of Matter, 6E
86
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Rearranging gives
2
0 .11(0 . 65611 . 62 x+ x )=x
Then put in form of quadratic equation
ax2 + bx + c = 0
2
0 . 072170. 1782 x +0 .11 x x=0
2
0 .11 x 1 . 1782 x+ 0. 07217=0
Solution for quadratic equation given by
b b 4 ac
x=
2a
2
Jespersen/Brady/Hyslop
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88
I
C
E
0.000
+0.064
+0.064
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0.810
0.064
0.746
0.810
0.064
0.746
[CH3CO2C2H5]equil = x = 0.064 M
Jespersen/Brady/Hyslop
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2H2(g) + O2(g)
Ex. 7 2H2O(g)
K c=
[ H 2 ] [O 2 ]
2
[ H 2O ]
Jespersen/Brady/Hyslop
=7. 310
18
90
2H2O(g)
2H2(g) + O2(g)
18
7 .310
0.00
+2x
+2x
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Initial
0.100
2x
Change
Equilm 0.100 2x
0.00
+x
+x
3
(2x ) x
4x
=
=
2
2
(0 .1002x ) (0 . 1002x )
91
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2H2 (g) +
O2 (g)
0.100
2x
0.100
0.00
+2x
+2x
0.00
+x
+x
7 .310
3
(2x ) x
4x
=
=
2 0 . 010
(0 .100 )
4x =0 . 010(7 . 310
Jespersen/Brady/Hyslop
18
) = 7.3 1020
92
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7. 310
x =
=1 . 81020
4
Now take cubic root
3
x= 1 .810
20
=2 . 610
x is very small
0.100 2(2.6107) = 0.09999948
Which rounds to 0.100 (3 decimal places)
[H2] = 2x = 2(2.6107)
= 5.2107 M
Jespersen/Brady/Hyslop
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dropped x term
0 . 05
Ci
Jespersen/Brady/Hyslop
94
Learning Check
I
C
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0
Q=
=0
2
(0 . 2)
Q<K shifts right
x = 1.41017
Q=
16
3 .510
PN
P
O4
2
NO
x
=
2
(0 . 2)
[B]= 1.41017 M
proof: 1.41017/0.2<0.05
Jespersen/Brady/Hyslop
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Your Turn!
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0.3 M
0.002 M
0.04 M
0.5 M
Jespersen/Brady/Hyslop
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Ex. 2a
H2(g) + I2(g) 2HI(g) @ 450 C
Initially H2 and I2 concentrations are 0.200
mol each in 2.00L (= 0.100M); no HI is
present
At equilibrium, HI concentration is 0.160 M
Calculate KC
To do this we need to know 3 sets of
concentrations: initial, change and
equilibrium
Jespersen/Brady/Hyslop
97