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CHEM 101 Tutorial L7

Chemical Equilibrium
1. Based on these descriptions, write a balanced equation and the corresponding
𝐾𝑐 expression for each reversible reaction.
a) Carbonyl fluoride, COF2(g), decomposes into gaseous carbon dioxide
and gaseous carbon tetrafluoride. 2 Cote EC02 CF4 t

k=
b) Peroxodisulfate ion, S₂O82-, oxidises iron(II) ion to iron(III) ion in
aqueous solution and is itself reduced to sulfate ion.
Ke=§% ?}
305*+2 E2S th
{¥
e't

g[

2. Write equilibrium constant expressions, 𝐾𝑐 , for the reactions.

a) 2 NO(g) + O2(g) ↔ 2 NO2(g)

Kc
a
b) Mg(OH)2(s) + CO₂(g) ↔ MgCO3(s) + 2 OH-(aq)

3. Write equilibrium constant expressions, 𝐾𝑝 , for the reactions.

CS2(g) + 4 H2(g) ↔ CH4(g) + 2 H₂S(g)

Kp= (RT)"
kp=K
4. Calculate the value of 𝐾𝑐 , from the 𝐾𝑝 value given.
2 NO(g) + O₂(g) ↔ 2 NO₂(g) 𝐾𝑝 = 1.48 × 104 at 184 ℃ n .
eat
4={0%2}%
"

" = 2 - f a tD = 2 - 3 = - 1
(Ry)-C-1 )
4 Kp =
1.48×104×(0.08206×457.154)=5,5×5×10
=

5
5. A mixture of 1.00 g H₂ and 1.06 g H₂S in a 0.500 L flask comes to equilibrium
at 1670 K: 2 H₂(g) + S2(g) ↔ 2 H₂S(g). The equilibrium amount of S2(g) found is
8.00 x 10-6 mol. Calculate the value of 𝐾𝑝 at 1670 K for pressures expressed in
atmospheres.

1
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First,calculate t h e
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partial pressures:
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'II I i ¥? "E)

Animates)= LIT ×II% ¥f[a% ×Ht =

peq.it
=nR t.ooxwbmho.fi?Ibtatm-m-
.
=

ktoD=2.iqxioItm
Chemicalequation: 2 I t , t Sz ④ I 2
His
Initial p : 136 a t m 0 atm 8 . 5 2 a t m

: t o - 0 0 4 3 8a¥n 0.00219 a t m
changes i nP
-0.00438 a t m *
EquilibriumP i 1 3 6 a t m o . o o2 1 9 a t m 8 . 5 2 a t m

values with
= = ¥9
N B : The
asterisks a r e s o
minutes
don't a d d
=

such t h a t they
t o 1 3 6a t i n a
significance
8 . 5 2d -w e w e r e ignored.
E ve n i f they a r e a d d e d ,y o u gett h e answer. s a m e
6. Compute 𝐾𝑐 for the reaction N₂(g) + O₂(g) + Cl2(g) ↔ 2 NOCl(g), given the
following data at 298 K.

① l 1
2
N2(g) + O2(g) ↔ NO2(g) Y 𝐾 =l 1.0 x 10 Y
𝑝
-9

1
NOCl(g) + 2 O2(g) ↔ NO2Cl(g) 𝐾𝑝 = 1.1 x 102

f : c
Reverse.. NqCI
1
NO2(g) + 2 Cl2(g) ↔ NO2Cl(g) * i t
𝐾𝑝 = 0.3

C →
NO ⑨t ¥02 K =
¥02
€mulhpbby2 2M¥ Kp=(¥io%¥of
p

③
2 noa +0% 3

2¥ tUz④E2NfEl kpilo.DZ
netin.III.IE?IEEEfkI=aoxioT
tippet)-KP,×Kpz×Kp,-_t.oxidfxg.IT/oyaXlo.35--
2
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=
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24
"$
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## "#$"
## $
"
=,Rk Kp (RT)-at
Kp Ke (RT) '9... Kc
=
NB. =
ae

A l l = 2 - ( H + I t1 )
= 2-3=-1

Kc = Kp(RT)-"= 744...× ,
5 G0 8 2 0 6 La t m mot'k '× 298k)-'
.

= 22

7. Equilibrium is established at 1000 K, where 𝐾𝑐 = 281 for the reaction 2 SO₂(g)

+ O2(g) ↔ 2 SO3(g). The equilibrium amount of O2(g) in a 0.185 L flask is
0.00247 mol. Predict the ratio of [SO₂] to [SO3] in this equilibrium mixture. constants
NB: f o r m o s t equilibrium reaction,alwaysstart
bywriting the equilibrium
I t c a n either b e K c o r Kp- ie. K c = {0%3}-0,3=2
81
i.
8 1
III. a xj.IE#mo f"

{% =
NB'.More steps needed
to
=
make th numerator.
e

8. An equilibrium mixture at 1000 K contains 0.276 mol H₂, 0.276 mol CO2, 0.224
mol CO, and 0.224 mol H₂O.
CO2(g) + H2(g) ↔ CO(g) + H2O(g)
a) Show that for this reaction, 𝐾𝑐 is independent of the reaction volume,
𝑉.

÷¥ i
a) Calculate the value of 𝐾𝑐 and 𝐾𝑝 .

a.

Therefore, K c i s independent
ofV.
This happens because
a .
* ,
b) Kp =
Ke CRT)% Kp = K e for this reaction because A l l = 0

°
Kp K c (RT)
=
= K cx I = K c

=
a --
3
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9. Predict if a mixture of 0.0205 mol NO2(g) and 0.750 mol N₂O4(g) in a 5.25 L flask at
25 ℃, is at equilibrium. If not, predict the direction in which the reaction will proceed-
toward products or reactants.
N₂O4(g) ↔ 2 NO2(g) 𝐾𝑐 = 4.61 × 10-3 at 25 °Creactant-
First,compute the value
o f ④ forthegivenamountso f product 12
votre
={wI = (comme value.)
m i
④ i .o f × , t o ke

=
Q e = I .07×154C 14=4.61×1?
I t Qc < Kc ,m e a n s t h e denominator (reactantconcentration) i s largerthant h e

numerator (product concentration). I n fact,t h e reaction willproceedt o t h e right,

that i s , toward products u n t i l equilibrium,k e , i established.
t h e activation energy,
time t o
AB: If E a, i s large,t h e reaction mayt a ke s o m e
reach equilibrium.
10. A mixture consisting of 0.150 mol H2 and 0.150 I2 is brought to equilibrium at
445 °C, in a 3.25 L flask. Calculate the equilibrium amounts of H₂, I2, and HI.
u s e I C E table
H2(g) + I2(g) ↔ 2 HI(g) 𝐾𝑐 = 50.2 at 445 °C
l e t K = and He o r I , t h a t reacts. T h e n u s e stoichiometryt o determine
t h e amounts
q H I fo r m e d i n t e r m s o f × , I finally solve fo r × . .
Chemical equation: H I
He + I , I
2
④
Initial amounts: 0 . I 50mA mA md

{k
0.150 0 . o o o

i n amounts MA
'

[ D .
- X - x mot t 2 x and
change
Equilibriumamounts'. 0.150- X 0.1 5 0 -X 2 2

=¥÷ .= ÷y ,

←
a .
not,#*,
= 7. 0 9 =
rice =
o?
x

2 x = i . 0 6 - 7.0 9 1
4¥
;

× =
0-117mA j . ' - Amount H I = 2 x =
=

4
of met
2 × 0,1 1 7
amount
Hz=amount I 2=101150-X)md= ④150-0117)md=
M¥1initial concentration c a n becalculated 0.033mA
instead'. CHD-IIif-ITIY-o.co#TstM
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11. 1.00 g each of CO, H₂O, and H₂ are sealed in a 1.41 L vessel and brought to
equilibrium at 600 K. Compute the amount, in grams, of CO2 that will be
present in the equilibrium mixture.
CO(g) + H2O(g) ↔ CO2(g) + H2(g) 𝐾𝑐 = 23.2
Compute
the i n i t i a l concentration present. T h edetermine
the equilibrium concentrations o fe a c h species
the m a s s 9- C02
of a l l species. Finally,compute "
present a t equilibrium. "

init
=
III-xfj.no?gI-o=o.oz=zm
'" "it--I xfgf-fff.jo#aymiatdmit=IITI?IfI--o m

= Coz t Hz
Equation: co t
Hyo
Initial c a r d i 0.0253M 0 . 0394M 0 . o o0 0M 0.352M

A conch : M M t h M
- x M - x + ×

{quit.a n d I 0.0 2 5 3 -X ) M (0.0394→ c )M 2 M f . 352 M

k=E I a i"

o.jo?IIIIII77xtF
O . O 231-I.5 0 × + 2 3 . 2 × 2 = 0 . 3527C TX2
2 2 . 2 × 2 - I .8 52 x t 0 . 0 2 3 1 = 0

× =
-b±r TT=-1-1.852/1531,35=2-05 7

= 0.0682M
Now see w e thatt h e1stvalue o f ×
gives
negative 12 3M

Concentrations
for reactants
I I . [CO3= 0.0 2 5 3 - 0 - 0 6 8 2 = - 0.
0429M 1
equilibrium
,
a t concentrations.
[µ 0.0394-0.0682 =- 02=8M
Thus,X
8

=
0,0153M =
[coz]
=

← molarm a s s

mass xI o
5
? i%÷=o

so.
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12. Exactly 1.00 mol each of CO and Cl₂ are introduced into an evacuated 1.75 L
flask, and the following equilibrium is established at 668 K.
CO(g) + Cl2(g) ↔ COCl2(g) 𝐾𝑝 = 22.5 (for pressures in atmospheres)
For this equilibrium, calculate: ideal
n R T
a) The partial pressure of COCl2. PV =
gasl a w
b) the total gas pressure.
i t : /
Their moler a t .
a ) Initial partialpressure of each gas:
Pco =
P%= n[ t.oomdxo.ogfffqatm
=

We have t o calculate
md-tk-txlbsk-3.at
organising
m

o u r calculation equilibrium partial pressures by

around the balanced
I C E chemical equation. Use a
table'.
22.5
Gmahmi.CO(g) Kp =
t 9 2 I
C 0 C
1ED
Initial P i 3 1.3 a t m 3 1.3a t m 0 atm
g p : - × atm
- a atm + × atm
[full. P : 3 1 . 3 - a a t m 31.3-× 2 atm
atm
kp=
i
a m
=
2 2 i t =

22.5 (979.7-62.6kt )

•
E)=X
2043-1408.5×+225×2 × 22043-1409.5×+2215×2=0
=
j
x
=-b±F n

=_fi4os ±T I T
i. x =
1409.5415T = 30.la#ntzatatmftEetaIIYfessII)
Thus, Pao = Paz 3 1 . 3 atm-30.14 a t m 1*16a t m j
=
=
Roof 3 0.1 4 atm
b ) Roti = R o t pgztpoq-I.lbatwttlbatmt3oitatm-32.tt#atm
6
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13. If the volume of an equilibrium mixture of N2(g), H2(g), and NH3(g) is reduced
by doubling the pressure, will 𝑃N2 have increased, decreased, or remained the
same when equilibrium is re-established? Explain.
If the total N₂(g) + 3 H2(g) ↔ 2 NH3(g)
compression,the
pressure of a mixture of gases a t equilibrium is doubledby
equilibrium w i l l miles of gas
t o counteractt h e Increase i n shift t ot h e s i d e with fewer
pressure.
2 N Its Thus,i ft h e
N fE¥¥+ I n n e s pressure o fa n
§

equilibrium mlXthk o f Nz
µ,
involving these gases w i l l proceed
,

¢
pityg ) I doubled,t h e reachi n
n e w theforward direction t o produce a
i n
equilibriummixture t h a t contains additional ammonia 1 less
molecular nitrogen 1 molecular
when
hydrogen. T h e Pw,will h a v e decreased
equilibriumi s re-established. The final
Pressure
f o rt h e N z will b e highert h a n i t s
equilibrium partial
original partial pressure
priort o the doublingo f t h e total pressure.
14. Explain how each of the following affects the amount present in an
equilibrium mixture in the reaction:
3 Fe(s) + 4 H2O(l) ↔ Fe3O4(s) + 4 H2(g) ∆𝑟 𝐻° = -150 kJ mol-1
Inches 4-m oles
temperature
a) Raising the temperature of the mixture; high s
This reactioni s exothermic with D rH o s o k J .Thus,
He
f a v o u r the reverse reaction(endothermic reaction). The amount 9-
,

present a t high temperatures w i l l b e lesst h a n that presenta t

l o w temperatures
b) introducing more H₂O(g) at constant volume;
Introducing
reactants involved. m o r e Hz0 wil
H20④ in o n e
of the
l

favouring products.
cause t h e equilibrium positiont o shift t ot h eright,
The a m o u n t o f Hz④ will i n c r e a s e .
c) doubling volume of the container holding the mixture; witht h e
Doublingt h e volume the container willfavour theside thereaction
of of
largest s u m stoichiometric coefficients.Thes u m of the
of gaseous
stoichiometric coefficients o fgaseous species i s t h e s a m e (4) o n bothsides
o f t h i s reaction. Therefore, Increasing
7
t h e volume t h e container
of
will have n o effect o n
t h e a m o u n t of Hz presen a t
equilibrium.
t
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d) adding an appropriate catalyst. reaction
A catalyst merely speeds t h e r a t e a t which
a

up
reachest h e equilibrium position. T h e addition o f a catalyst
h a s n o e f fe c t o n t h e amount o f I t , presen a t equilibrium. t

15. For the reaction C₂H₂(g) + 3 H₂(g) ↔ 2 CH4(g), the equilibrium constant is 𝐾𝑐 =
4.9 X 10-11 at 1100 K. In an experiment, 0.100 mol C₂H₂ and 1.00 mol H₂ are
added to an otherwise empty 5.00 L container, and the temperature is raised
to 1100 K. Calculate the equilibrium concentration of CH4. U s et h e I C E table.
Calculate t h e initial concentration each species
of present2 u s et h e I C E
table t o solve for t h e final a n s w e r .
Let ' x ' b e the

|
[ Hit, =
IY0-1TI 0 . 0 2 0 M =
concentration
t

change i n
[H23i n i t 1 because I ts
= ooomI =-
0.200M of GH2
coefficient i s 1 .
[CH4)i n i t = 0 M 14=4.9×15"
Equation: GHz t 3 Hz = 2 city a t 1l o o k
O M
I nthat conch , 0 2 0 M 0 . 2 0 0M
'
0 .

D in Cont: - a M - 3 >C M + 2 x M

[quit. Cohen: 0 . O20-2CM 0.2 N - 3 2 M 2 x M

substitutingt h e equilibriumconcentration, from
K, = §fg fj ,

t h e I C E table into the K . expression:

w e a r e dealingwith a
× ← C 0.020M
"no
verys m a l l K value.
Now,let's a s s u m e
M , then that
o r O '2 0 0
0,0 2 0 - × =
f . you-3×3 w i l l maket h e calculationm o r e 0 , 0 2 0I
0.200-3×2 0 . 2 0 0
complex,now w e havesimplifiedi t .
4.9×15" = go.IO#o.ToIz--
4×2 = coIIoTEoosT=IIToI)
(4.9×1511)(0.000/6)=(4.9×10-11) (1.6×10-4) = (4.9×16)×15" 784×151

4¥ =
7 to'5 fE=f 8
F
2=4.43-8M
-
'

.
The equilibrium concentrationofcity,[cHyJeqµ=2×M= 2144272×158)M
=-8.85×-1581