1

Chapter 15 - Homework Solutions

15.3)
The following diagram represents an equilibrium mixture for a reaction,
A + X AX
(Copyright by Prentice Hall)
Red = A Blue = X Red-Blue = AX
If the volume is 1 L, is K greater or smaller than 1?
Since the question gives us volume but no other info we will assume this is K
c
.
This means we need molar concentrations. While we specifically have particles
this is related to moles and mole ratios and particle ratios are the same. So we can
use the number of particles in place of moles to determine molarities.
[A] = 3/1L = 3 M [X] = 2/1L = 2 M [AX] = 8/1L = 8 M
[AX] 8 8
K
c
= ----------- = ----------- = ----- = 1.33
[A] [X] (3) (2) 6
2
15.6)
The reaction A
2
+ B
2
2 AB has an equilibrium constant K
c
= 1.5 . The
diagrams below represent reaction mixtures containing reactants and products.
(Copyright by Prentice Hall)
Red = A
2
Blue = B
2
Red-Blue = AB
[AB]
2
K
c
= ------------- = 1.5
[A
2
] [B
2
]
Express the contents in the boxes in terms of concentrations (molarities as in
15.3 above). Need to calculate the reaction quotient, Q
c
, and compare to K
c
.
Remember, products in numerator, reactants in denominator
Q = K at equilibrium
Q > K not at equil.: numerator too large, denominator too small
Too much product, not enough reactant to be at equilibrium
- reaction must proceed from right to left in the reverse
direction toward reactant to reach equil. (use reactant &
produce product)
Q < K not at equil.: numerator too small, denominator too large -
Not enough product, too much reactant, to be at
equilibrium - reaction must proceed from left to right in
the forward direction toward product to reach equil. (use
reactant & produce product)
3
15.6) (cont.)
a) & b) Which reaction(s) are at equilibrium and if not what direction do the
proceed to reach equilibirum?
Mixture 1: 1 A
2
, 1 B
2
, 6 AB
[AB]
2
(6)
2
Q
c
= ------------- = ---------- = 36
[A
2
] [B
2
] (1) (1)
Q
c
> K
c

36 > 1.5
The mixture is not at equilibrium. Since Q is larger than K there is too much
product and the reaction proceeds to the left (reverse direction) toward
reactants.
Mixture 2: 3 A
2
, 2 B
2
, 3 AB
[AB]
2
(3)
2
Q
c
= ------------- = ---------- = 1.5
[A
2
] [B
2
] (3) (2)
Q
c
= K
c

1.5 = 1.5
The mixture is at equilibrium.
Mixture 3: 3 A
2
, 3 B
2
, 2 AB
[AB]
2
(2)
2
Q
c
= ------------- = ---------- = 0.44
[A
2
] [B
2
] (3) (3)
Q
c
< K
c

0.44 < 1.5
The mixture is not at equilibrium. Since Q is smaller than K there is too
much reactant and the reaction proceeds to the right (forward direction)
toward products.
4
15.7)
The reaction A
2
(g) + B(g) A(g) + AB(g) has an equilibrium constant K
p
=
2 . The diagram below shows a mixture containing A atoms, A
2
molecules and AB
molecules.
(Copyright by Prentice Hall)
Red = A atoms Blue = B atoms Red-Blue = AB molec.
How many B atoms should be shown in the diagram if the system is at equilibrium?
You are given K
p
but since )n=0 (change in moles of gas) K
p
= K
c
. It is easier to
work the problem using K
c
. As in 15.3, we can use the # particles in place of # of
moles for molarity. Thus we have [A] = 2 M, [AB] = 4 M, [A
2
] = 2 M. We want to
determine [B]. Solve K
c
expression for [B].
K
p
= K
c
. since )n = 0 ()n = mol gaseous products - mol gaseous
reactants)
[A] [AB]
K
c
= ------------- = 2
[A
2
] [B]
[A] [AB] (2) (4)
[B] = ------------- = --------- = 2 M
[A
2
] K
c
(2) (2)
Therefore, 2 Bs (blue spheres) should be added to the diagram.
5
15.9)
The reaction A
2
(g) + B(g) A(g) + AB(g) is at equilibrium. The diagrams
below show mixtures containing A atoms, B atoms, A
2
molecules and AB
molecules at 300 K (diagram a) and 500 K (diagram b).
(Copyright by Prentice Hall)
Red = A atoms Blue = B atoms
Is the reaction exothermic or endothermic?
For temperature changes you treat heat as a reactant or product. Also, changes in
temperature are the only changes that cause a numerical change in the
equilibrium constant, K.
Remember:
)H < 0 (-); exothermic; heat is a product
- inc T (add heat, a product), shift left (K dec)
- dec T (remove heat, a product), shift right (K inc)
Reactants Products + Heat
)H > 0 (+); endothermic; heat is a reactant
- inc T (add heat, a reactant), shift right (K inc)
- dec T (remove heat, a reactant), shift left (K dec)
Heat + Reactants Products
* continued on next page *
6
15.9) (cont.)
)H < 0 )H > 0
T 8, 7, K 9 T 8, 6, K 8
T 9, 6, K 8 T 9, 7, K 9
T & K move in T & K move in
opposite direction same direction
Product favored by Product favored by
LOW T HIGH T
When it says product is favored by low T it means that low temperature produces
more product. When it says product is favored by high T it means that high
temperature produces more product. In neither case does it mean that we always
want product. There are times we dont want product (for instance, if going from
reactant to product means an explosion we dont want product to form).
Diagram (a), 300 K:
[A] = 3 M, [AB] = 5 M, [A
2
] = 1 M, [B] = 1 M
[A] [AB] (3) (5)
K
c
= ------------- = ---------- = 15
[A
2
] [B] (1) (1)
Diagram (b), 500 K:
[A] = 1 M, [AB] = 3 M, [A
2
] = 3 M, [B] = 3 M
[A] [AB] (1) (3)
K
c
= ------------- = ---------- = 0.333
[A
2
] [B] (3) (3)
Since K
c
decreases as T increases (move in opposite directions) this means the
reaction is exothermic (shifts to left, reverse direction, as temp. inc.).
7
The following are some general comments about equilibrium and its relationship to
rates, rate constants and concentrations of reactants and products.
8
15.12)
9
15.13)
10
15.16)
11
15.18)
This problem relates K
p
and K
c
. They are not necessarily numerically equal. A
relationship can be derived between the two, assuming ideal gas behavior. The
following is the derivation for the balanced equation given , but holds in general.
a A (g) + b B (g) x X (g) + y Y (g)
[X]
x
[Y]
y
K
c
= -------------
[A]
a
[B]
b
(P
X
)
x
(P
Y
)
y
K
p
= ---------------
(P
A
)
a
(P
B
)
b
Assuming IGL behavior: P
A
= (n
A
/V) RT = (M
A
) RT
P
A
= [A] RT
Substitute this for each partial pressure in K
p
([X] RT)
x
([Y] RT)
y
[X]
x
[Y]
y
(RT)
x
(RT)
y
K
p
= -------------------------- = ---------------------------
([A] RT)
a
([B]) RT)
b
[A]
a
[B]
b
(RT)
a
(RT)
b
= K
c
(RT)
{(x +y) - (a + b)}
K
p
= K
c
(RT)
)n
)n = {(x +y) - (a + b)} (Change in moles of gas).
mol gas mol gas
product reactant
R = 0.08206 LCatm/molCK, T in Kelvin
Calculate K
c
at 303 K for SO
2
(g) + Cl
2
(g) SO
2
Cl
2
(g) given K
p
=34.5
n = 1 & (1 +1) = &1
K
c
= K
p
(RT)
&)n
= (34.5) {(0.0821 LCatm/molCK)(303 K)}
& (& 1)
= (34.5) (24.86418)
= 857.81 = 858
12
15.21)
SO
2
(g) + 1/2 O
2
(g) SO
3
(g) (1)
K
p
= 1.85 at 1000 K
P
SO3
K
p1
= -----------------
(P
SO2
) (P
O2
)
1/2
When you multiply a rxn by some factor the K for the new rxn is equal to original
K raised to the power of the factor the rxn was multiplied by (the multiplier).
Proof
a A + b B W x X + y Y (1)
[X]
x
[Y]
y
K
1
= -------------
[A]
a
[B]
b
Multiply by n
(aCn) A + (bCn) B W (xCn) X + (yCn) Y (2)
[X]
xn
[Y]
yn
[X]
x
[Y]
y
K
2
= --------------- = (-------------)
n
= K
1
n
[A]
an
[B]
bn
[A]
a
[B]
b
Multiply by -1 reverses rxn.
- a A + - b B W - x X + - y Y
want (+) coeff - like in math switch reactants & products to other sides
x X + y Y W a A + b B
K
rev
for rev. rx is 1/K
for
or (K
for
)
&1
(reciprocal of K
for
for the forward rx)
K
rev
= (K
for
)
&1

13
15.21) (cont.)
a) Calculate K for the reverse rxn, K
rev
SO
3
(g) SO
2
(g) + 1/2 O
2
(g) (2)
(P
SO2
) (P
O2
)
1/2
1
K
rev
= ----------------- = ------ = (K
for
)
&1
P
SO3
K
for
K
rev
= 1/(1.85) = 0.54054 = 0.541
b) Calculate K for the following reaction:
2 SO
2
(g) + O
2
(g) 2 SO
3
(g) (3)
This is equation (1) multiplied by a factor of 2.
(P
SO3
)
2
K
p1
= ----------------
(P
SO2
)
2
(P
O2
)
K
p3
= (K
p1
)
2
= (1.85)
2
= 3.4225 = 3.42
c) Calculate K
c3
(for reaction (3) in part b).
Need )n: )n = 2 & (2 +1) = &1
K
p
= K
c
(RT)
)n
K
c
= K
p
(RT)
&)n
= (3.4225) {(0.0821 LCatm/molCK)(1000 K)}
& (& 1)
= (3.4225) (82.1)
= 280.987
= 281
14
15.23)
Find K for a reaction that is the sum of two reactions.
A (aq) + B (aq) W C (aq) K
1
= 1.9 x 10
-4
C (aq) + D (aq) W E (aq) + A (aq) K
2
= 8.5 x 10
2
-----------------------------------------------------
B (aq) + D (aq) W E (aq) K
3
If two rxns (eqns) can be added to give a 3
rd
rxn (eqn) then K
3
is the product of
the K
1
and K
2
.
R
x1
+ R
x2
= R
x3
K
1
* K
2
= K
3
[C] [E] [A] [E]
---------- * ---------- = ---------- ([C] and [A] cancel out)
[A] [B] [C] [D] [B] [D]
For the reactions given we have the following:
CoO (s) + H
2
(g) W Co (s) + H
2
O (g) K
c1
= 67
CoO (s) + CO (aq) W Co (s) + CO
2
(g) K
c2
= 490
15
15.23) (cont.)
We need to turn eqn 2 around (reverse it) so the CO
2
is a reactant and the CO is a
product. This means K
c2, rev
= K
c2
!1
. We add the eqns and cancel things that appear
on both sides.
CoO (s) + H
2
(g) W Co (s) + H
2
O (g) K
c1
= 67
Co (s) + CO
2
(g) W CoO (s) + CO (aq) K
c2, rev
= 1/490
----------------------------------------------------------
H
2
(g) + CO
2
(g) W CO (aq) + H
2
O (g) K
3
K
3
= K
c1
* K
c2, rev
= (67) (1/490)
= 0.13673
= 0.14
16
15.25)
2 Hg
2
O (s) 4 Hg (R) + O
2
(g)
What would K
c
look like if you included everything (including pure solid and liq)?
[Hg]
4
[O
2
]
K
c
= --------------
[Hg
2
O]
2
However, we normally exclude pure solids and liquids. Their molar conc. are
essentially constant so their conc. are incorporated into the equilibrium constant.
K
c
[Hg
2
O]
2
K
c

= --------------- = [O
2
]
[Hg]
4

K
c
= [O
2
]
a) The same thing is done for K
p
(ignore solids and liquids).
K
p
= P
O
2
b) As noted above, the molar concentrations for solids and liquids are constant.
Their concentration is a ratio of moles to volume occupied (which is related
to their density). This doesnt change whether you have a small or large
amounts.
NOTE:
PURE SOLIDS and LIQUIDS do NOT appear in the expression for K or Q.
(Aqueous and gaseous substances should be in K or Q.)
17
15.27)
2 HI (g) H
2
(g) + I
2
(g)
At 425C,
[HI] = 3.53 x 10
&3
M
[H
2
] = 4.79 x10
&4
M
[I
2
] = 4.79 x 10
&4
M
[H
2
] [I
2
] (4.79 x10
&4
) (4.79 x10
&4
)
K
c
= ------------- = -------------------------------- = 0.01841 = 0.0184
[HI]
2
(3.53 x 10
&3
)
2
18
15.30)
15.32)
Given initial conc. and asked for K
Set up an Equilibrium Table (ICE table)
This table should be done in Molarity (M) or Pressure (atm)
If you use moles in the table you must convert the moles to conc. (M) or
pressure (atm) before substituting into the expression for K.
* See Next Page *
19
15.32) (cont.)
20
15.34)
21
15.36)
22
15.38)
N
2
(g) + 3 H
2
(g) 2 NH
3
(g)
(P
NH
3
)
2
K
p
= --------------- = 4.51 x 10
!5
at 450 C
(P
N
2
) (P
H
2
)
3
(Q
p
has the same form)
a)
P
NH
3
= 98 atm, P
N
2
= 45 atm, P
H
2
= 55 atm
(P
NH
3
)
2
(98)
2
Q
p
= --------------- = -------------- = 1.282 x 10
!3
= 1.3 x 10
!3
(P
N
2
) (P
H
2
)
3
(45) (55)
3
Q
p
> K
p
too much product, not enough reactant; the reaction shifts left
toward reactants (reverse direction) to achieve equilibrium.
b)
P
NH
3
= 57 atm, P
N
2
= 143 atm, P
H
2
= 0 atm (no H
2
)
(P
NH
3
)
2
(57)
2
Q
p
= --------------- = -------------- = 4
(P
N
2
) (P
H
2
)
3
(143) (0)
3
Q
p
> K
p
too much product, not enough reactant; the reaction shifts left
toward reactants (reverse direction) to achieve equilibrium. This
one should be obvious. There is no H
2
(a reactant) initially. The
only way to get H
2
and reach equil. is for the reaction to move
left. As NH
3
decomposes H
2
forms. There must be some H
2
present to be at equil.
c)
P
NH
3
= 13 atm, P
N
2
= 27 atm, P
H
2
= 82 atm
(P
NH
3
)
2
(13)
2
Q
p
= --------------- = -------------- = 1.135 x 10
!5
= 1.1 x 10
!5
(P
N
2
) (P
H
2
)
3
(27) (82)
3
Q
p
< K
p
not enough product, too much reactant; the reaction must shift to
right toward products (forward direction) to achieve
equilibrium.
23
15.39)
SO
2
Cl
2
(g) SO
2
(g) + Cl
2
(g)
[SO
2
] [Cl
2
]
K
c
= ---------------- = 0.078 at 100C
[SO
2
Cl
2
]
Given K
c
and molarities of SO
2
Cl
2
and SO
2
. Want partial pressure of Cl
2
.
[SO
2
] = 0.052M
[SO
2
Cl
2
] = 0.108 M
Easiest thing to do is to find conc. of Cl
2
, [Cl
2
], and then its partial pressure.
[SO
2
Cl
2
] K
c
(0.108) (0.078)
[Cl
2
] = ---------------- = --------------------- = 0.162 M
[SO
2
] [Cl
2
] (0.052)
Use Ideal Gas Law, PV = nRT
P
Cl
2
= (n/V) RT = (M) RT = [Cl
2
] RT = (0.162 M)(0.08206 atm/MCK)(373K)
= 4.958 atm = 5.0 atm
15.41)
24
15.41) (cont.)
b) H
2
(g) + I
2
(g) 2 HI (g) K
c
= 55.3 at 700 K
An equilibrium mixture in a 2.00-L flask has 0.056 g H
2
and 4.36 g I
2
. What
is the mass of HI in the flask?
0.056 g H
2
1 mol H
2
[H
2
] = --------------- ------------------ = 0.013889 M = 0.014 M
2.00 L 2.01588 g H
2
4.36 g I
2
1 mol I
2
[I
2
] = ------------- -------------------- = 0.008589 M = 0.00859 M
2.00 L 253.80894 g I
2
[HI]
2
K
c
= ------------
[H
2
] [I
2
]
[HI] = {K
c
[H
2
] [I
2
]}
1/2
[HI] = {(55.3) (0.013889) (0.008589)}
1/2
[HI] = 0.081223 = 0.081 M
0.081223 mol HI 127.9124 g HI
? g HI = 2.00 L ----------------------- --------------------
1 L soln 1 mol HI
= 20.779
= 21 g HI
25
15.44)
Calculate the initial conc. of Br
2
and Cl
2
and use equil. (ICE) table to find equil. conc.
[Br
2
] = [Cl
2
] = 0.25 mol/1.0 L = 0.25 M
ICE Table - In MOLARITY (or atm when K
p
involved)
Br
2
(g) + Cl
2
(g) W 2 BrCl (g)
Initial 0.25 M 0.25 M 0
Change ! x ! x + 2x
------------------------------------------------------
Equil (0.25 ! x) (0.25 ! x) 2x
[BrCl]
2
K
c
= --------------- = 7.0
[Br
2
] [Cl
2
]
(2x)
2
(2x)
2
K
c
= --------------------------- = --------------- = 7.0
(0.25 ! x) (0.25 ! x) (0.25 ! x)
2
This eqn is a perfect square - we can take the square root of both sides.
(2x)
--------------- = (7.0)
1/2
= 2.645
(0.25 ! x)
2.645 (0.25 ! x) = 2x
0.6614 ! (2.645)x = 2x
0.6614 = (4.645)x x = 0.1423 = 0.14 M
[Br
2
] = (0.25 ! x) = (0.25 ! 0.1423) = 0.1076 = 0.11 M
[Cl
2
] = (0.25 ! x) = (0.25 ! 0.1423) = 0.1076 = 0.11 M
[BrCl] = 2x = 2 (0.1423) = 0.2847 = 0.28 M
Check: K
c
= (0.2847)
2
/(0.1076)
2
= 7.0
26
15.46)
Solid NH
4
HS is placed in a closed container and decomposes until equilibrium is
reached. What are the concentrations of NH
3
and H
2
S at equilibrium?
NH
4
HS (s) W NH
3
(g) + H
2
S (g)
initial C 0 M 0 M
change -x + x + x
-----------------------------------------------------------------------
equil constant + x + x
K
c
= [NH
3
] C [H
2
S] = 1.2 x 10
-4
NH
4
HS (s) doesnt appear in K
(pure solids and liquids do not
x
2
= 1.2 x 10
-4
appear in K)
x = (1.2 x 10
-4
)
1/2
= 1.0954 x 10
-2
M
[NH
3
] = [H
2
S] = 1.1 x 10
-2
M
15.47)
a) Solid CaSO
4
is placed in a closed container and decomposes until equilibrium
is reached. What are the concentrations of Ca
2+
and SO
4
2&
at equilibrium?
CaSO
4
(s) W Ca
2+
(aq) + SO
4
2&
(aq)
initial C 0 M 0 M
change -x + x + x
-------------------------------------------------------------------------
equil constant + x + x
K
c
= [Ca
2+
] C [SO
4
2&
] = 2.4 x 10
-5
CaSO
4
(s) doesnt appear in K
(pure solids and liquids do not
x
2
= 2.4 x 10
-5
appear in K)
x = (2.4 x 10
-5
)
1/2
= 4.8989 x 10
-3
M
[Ca
2+
] = [SO
4
2&
] = 4.9 x 10
-3
M
27
15.47) (cont.)
b) What is the minimum mass of CaSO
4
(s) needed to reach equil. in 3.0 L of soln.?
A saturated soln of CaSO
4
(aq) is 4.9 x 10
-3
M (this is the dissolved amount of
CaSO
4
, which is [Ca
2+
] = [SO
4
2&
])
4.9 x 10
-3
mol 136.14 g CaSO
4
? g CaSO
4
= 3.0 L soln ------------------- ---------------------- = 2.0 g CaSO
4
1 L soln 1 mol CaSO
4
15.49)
I
2
(g) + Br
2
(g) W 2 IBr (g) K
c
= 280 at 150C
The reaction is started with 0.500 mol IBr in a 1.00-L flask. Since no I
2
or Br
2
are
present initially the reaction proceeds in the reverse direction (right to left) toward
the reactants. Need to set up an ICE table. Since the reaction goes in the reverse
direction the negative x is on the right-hand side of the table and the plus xs go on
the left-hand side.
[IBr] = 0.500 mol/1.00 L = 0.500 M
I
2
+ Br
2
W 2 IBr
initial 0.000 0.000 0.500
change + x + x & 2x
-------------------------------------------------------------
equil x x 0.500 & 2x
[IBr]
2
(0.500 & 2x)
2
(0.500 & 2x)
2

K
c
= ------------- = ------------------- = ------------------ = 280
[I
2
] [Br
2
] (x) (x) x
2
Even though the reaction is going right to left (reverse direction), you still write K
c
for the balanced equation as written. That is the equation the given K
c
refers to.
* continued on next page *
28
15.49) (cont.)
(0.500 & 2x)
2

------------------ = 280 perfect square (take square root of both sides)
x
2
(0.500 & 2x)
----------------- = (280)
1/2
= 16.733
x
0.500 & 2x = (16.733) (x)
0.500 = (16.733) x + 2x
0.500 = (18.733) x
x = 0.02669 M
[I
2
] = [Br
2
] = 0.027 M
[IBr] = 0.500 & 2 (0.02669) = 0.44661 M = 0.447 M