CHEM1001 Lecture 30 Worksheet

1. Calculating Equilibrium Compositions

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2 2
2
c
CO H
K
CO H O
=


CO + H
2
O

CO
2
+ H
2

Initial 6.0 8.0 0 0
Change
-x -x +x +x
Equilibrium
6.0-x 8.0-x +x +x

( )( )
2.0
6.0 4.0
c
x x
K
x x

= =


( )( )
2
2
2
2
2.0 6.0 8.0
96.0 28.0 2.0
28.0 96.0 0
0
x x x
x x
x x
ax bx c
=
= +
+ =
+ + =

a =1, b =-28.0, c =96.0

2 2
2 2
4 28.0 28.0 4 1 96
24.0
2 2
4 28.01 28.0 4 1 96
4.0
2 2
b b ac
x
a
or
b b ac
x
a
+ + +
= = =
+
= = =


As we cant have 24 M CO
2
and 24 M H
2
(or more importantly we cant have 6.0-24 =-18
M CO), the physically reasonable answer is x =4.0

[CO
2
] =[H
2
] =x =4.0 M [CO] =6.0 x =2.0 M [H
2
O] =8.0 x =4.0 M.
(Check K
c
=4.0
2
/(2.04.0) =2.0.)


2. Calculating Equilibrium Compositions

[N
2
O
4
]
initial
=0.0240 mole/0.372 L =0.0645 mol L
-1
; [NO
2
]
initial
=0


N
2
O
4

2 NO
2

Initial concentrations 0.0645 0

Change in conc. -x +2x

Equilibrium concentrations 0.0645 - x +2x

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( )
2 2
2 3
2 4
2
4.61 10
0.0645
c
NO x
K
N O x

= = =

( )
2 3
2 4 3
2 3 4
4 4.61 10 0.0645
4 2.973 10 4.61 10
4 4.61 10 2.973 10 0
x x
x x
x x

=
=
+ =

( )
( )
2
3 3 4
2 3 3
3
2
3 3 4
2 3 3
3
4.61 10 4.61 10 4 4 2.973 10
4 4.61 10 4.779 10
8.065 10
2 2 4 8
4.61 10 4.61 10 4 4 2.973 10
4 4.61 10 4.779 10
9.217 10
2 2 4 8
b b ac
x
a
or
b b ac
x
a

+
+ +
= = = =

= = = =

As we cant have a negative concentration of NO
2
, the physically reasonable answer is x =
8.065 10
-3
. Hence [NO
2
] =2x =0.0161 M [N
2
O
4
] =0.0645 x =0.0564 M.
(Check K
c
=0.0161
2
/0.0564 =4.60 10
-3
)

3. Finding Approximate Equilibrium Compositions

Find the equilibrium concentrations of all species present at 2400K in the system

N
2
+O
2

2 NO K
c
= 2.5 10
-3
(at 2400K) (1)


N
2 +
O
2

2 NO


Initial concentrations 0.040 0.030 0

Change in conc. -x -x +2x

Equilibrium concentrations 0.040-x 0.030-x +2x


Write out the equilibrium expression in terms of x and then write out and solve the
quadratic expression.

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( )
( )( )
2 2
3
2 2
2
2.5 10
0.040 0.030
c
NO x
K
N O x x

= = =


( )( )
2 3
2 6 4 3 2
2 4 6
4 2.5 10 0.040 0.030
4 3.0 10 1.75 10 2.5 10
3.9975 1.75 10 3.0 10 0
x x x
x x x
x x

=
= +
+ =

( )
( )
2
4 4 6
2
4
2
4 4 6
2
4
1.75 10 1.75 10 4 3.9975 3.0 10
4
8.45 10
2 2 3.9975
1.75 10 1.75 10 4 3.9975 3.0 10
4
8.88 10
2 2 3.9975
b b ac
x
a
or
b b ac
x
a

+
+
= = =

= = =

Choose the physically plausible (positive) x, so [NO] =2x =1.7 10
-3
M; [N
2
] =0.040 x
=0.0392 M [O
2
] =0.030 x =0.0292 M.

The small equilibrium constant favours reactants. We expect x to be small.

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( )
( )( )
2 2
3
2 2
2 3
3
2 7
7 4
2
2.5 10
0.040 0.030
4 2.5 10 0.040 0.030
2.5 10 0.040 0.030
7.5 10
4
7.5 10 8.7 10
c
NO x
K
N O
x
x
x

= = =
=

= =
= =


[NO] =2x =1.7 10
-3
M; [N
2
] =0.040 M [O
2
] =0.030 M.
The two results are almost identical for [NO]. As x is so small, the initial concentrations of
N
2
and O
2
are close to their equilibrium concentrations.
The critical approximation is that little product is formed compared to the amount of
reactant present. In other words, 0.040-x 0.040, and 0.030-x 0.030.
This would not work for K >1 as the initial and equilibrium concentrations of reactants
would be too different.