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SCH4U: Chemical Equilibrium

(Text Ref. pg. 429-433)

1a)

What is a quantitative

1b)

What must be true of a chemical system such as the decomposition of CaC03(s) if it is to be

considered a Quantitative reaction?

Co.co, r
f\ \\
1c)

(c.ltl.

N\

(!!,")

~\

(S)

"rQc

Co,

-;

''3'

If',

(\

What happens to the CaC03(s) reaction if the system is closed and the CO2 is not allowed to
escape?

Tk
1d)

Co, 0

--'7

reaction?

(CtI.,\

"t r ,,-os.e.5.

lha.

o..\\~Yj

~ <2..'IICLlSe.

r "

r~\::Q

~o..c..a..

What conditions are required for us to assume a state of dynamic equilibrium?

0-\n
- (o(\"t(),l"\1

~~s.Qd

~'I~~<;LfV\

L'rO'b.C.e~il

1"1'1

"

\lle

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Du \' ,,~

?r.!.,:>

f'CL ')

2)

Consider the reaction: N204(g)

a)

Sketch a graph of Concentration of Reactants and Products vs Time for both experiments,

2N02(g) and the data in Table 2 (pg, 431)

Exper iment 2

Exper iment 1

).

N 04
2
-

---0, o~'6M
411t

'Y

-0.721

2N02
0

0, 1~

Cone.
(mol/L)

2~?2
-

~ N2~'4

~)(

-4 'X.

0_ '1;J ""

Cone.
(mol/L)
'l Hi'::>

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~ 0.034

o.(Jll,

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...../

'/I(tj')

1'1;;"\J~

a.1~
-------'~

b)

'

Time

State the generalization that experiments such as these have demonstrated regarding reversible
reactions in closed systems.

THE EQUILIBRIUM CONSTANT: Kc vs Kp

So far we have been considering the equilibrium constant (K.q) in terms of the equilibrium
concentrations of the reactants and products. This form of Keq is often referred to as Kc

However, the concentration of a gas is proportional to the pressure of that gas. So in equilibria
involving gases, the concentration of each gas in the system is proportional to the partial
pressure of each gas in the system. ie: [N2l a pN2' [H2l a pH2 and [NH3l a pNH3
Therefore, for systems involving gases, Keq can also be expressed in terms of the partial
pressure of each gas at equilibrium, or Kp.

Generally, K, '* Kp , but they both have all the properties of Keq and are constant at constant
temperature.
Problems:
1)
Write the Keq expression for each of the following equilibria as K, and Kp:
U.\-\Lq

'l..

a)
b)
c)

H2(g) + CI2(g) ..2HCI(g) = It 1[ u J

2NO(g) + 02(g) ..2N02(g)
Ill.
f >2N20S(g) ..4N02(g) + 02(g)

2)
a)
b)

Consider the following equilibrium system: 2NO(g) + CI2(g) ..2NOCI(g)

\:::1-' . ~~ "\)0"\1Write the Kp expression for this system
r
'l.. r
:\
At a given temperature, the partial pressures of the gases in an equilibrium mixture of lV\--lc:i-S \....~C.\l
this system are determined to be: pNO 66kPa, pCI2 18kPa and pNOCI 15kPa.
Determine the value of Kp for this system. l ().100C}CY~

3)
a)
b)

At 25C, Kp = 7.04x10-2 for the following system: 2N02(g) ...

N204(g).
If pN02 at equilibrium is 15kPa, determine the pN204 . \. \ ':l .~ kilo.")
If total pressure is equal to the sum of the partial pressures, determine the total pressure
of this system at equilibrium? ( '?la. ~ \<.~q.')

4)

Baking soda when heated decomposes in the following reaction:

2NaHC03(s) . Na2C03(s) + CO2(g) + H20(g)
-1'1

a)
b)
c)
d)
e)

t)<

+)(

+)1.

Consider the stoichiometry of this system in terms of "x"

Write, the K, and the K, expressions for this heterogeneous system. k,: [LC\2] 0116] k
If at 125C, the K, for this system is 2.4x10"". Determine the equilibrium
concentrations of [C02] and [H20]. O. I.J \10 ~ ~ 1'110 \ I L
At the same temperature, the Kp is 2.6x1 03 Determine the pH20 and the pC02 in this
equilibrium system (in kPa). 'l"\ ~Yo...
At equilibrium, what is the total pressure of the system at equilibrium?
\\J) \

0..

= (~

(Ol') (p \-it 0)

Keq and HETEROGENEOUS EQUILIBRIA

Reactions in which the chemical components exist in more than one physical state are referred
to as heterogeneous reactions. For example the decomposition of solid calcium carbonate:

If we consider the equilibrium constant for this system we find:

KeQ= [CaOJ[C0 1
[CaC03]
2

But, as we have discussed before, the concentrations of pure liquids and pure solids at
constant temperature are proportional to their densities, which are constant and independent of
the amount of the solid or liquid. In these reactions, the "concentration" of the pure solid or
liquid is considered as part of the "nature of reactants" and is incorporated into the K constant.
:. since [CaC03]

= constant

and [CaO]

= constant

If we re-arrange the KeQexpression to isolate all constants into the K constant:

K[CaC031 = [C02]
[CaO]
Problems:
1)

Write the Keqexpression for each of the following equilibria:

a)
b)
c)
d)
e)
f)
g)

2Hg(l) + CI2(g) H92CI2(s) '/tt.h'\

H20(I) H20(g)
\::1-l,t>J
...r.
5CO(g) + 1205(s) 12(g)+ 5C02(g) C\ ...lll\)11 (to')Ca(HC03Maq) CaC03(s) + H20(I) + CO2(g)
CaO(s) + S02(g) CaS03(s)
PbCI2(s) Pb2+(aq) + 2CI1(aq)
CH3COOH(aq) + H20(I) .CH3C001(aq) + H301+(aq)

2)

The density of water is 1.00 g/mL, determine the "molar concentration" of:
a) 18.0 mL of water, 100.0 mL of water.

3)

The density of solid CaC03 is 2.71 g/cm3 (1 ern" = 1 mL). What is the "molar
concentration" of:
a) 10.0 9 of solid CaC03
b) 35.0 9 of solid CaC03

?/

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SCH4U - Chemical
LeChatelier's

Equilibrium

and LeChatelier's

Princiole

Principle states:

A stress is defined as any introduced change that will effect the rate of the chemical reactions
involved. As such, the followinq factors mav be used to stress an eauilibrium system:

1)

Consider the following equilibrium system:

(Blue\

(Pink)

1ll\ -]

J
t

FO.~IHjr~ FwD

Lq-j

hV\)\Jf.:tSo

~"2-()]

1 [H2O]

ff\lfo\)a~
ri''I"tll\~

\\J'r\\

r~rI

'f">-n

\\..lrry

F~I'\

f",Y\

lurn

~t:\{

R'i(\

R'1

FI\-\J'DvR5

~ i~

2)

Observed Change
in System

System Response
to offset stress

Applied Stress

["'''

~"1\

I\J(II

\f""~

'vrl)

h\\)Q..

rt'\af CL

\')if'lk

rrvore,

b \UlLf
fnOf"1l.

i'Y)t\\'Q.

pI'" k
b.\"u

Changes in [components]
in new Equilibrium

L?ll

[J''J l'

~Rl1'

[PJJ-

[rl

LRji

(J'1 \.

2N02(g) "'" 'N20Ag) !::'s:(Brown)

(Colourless)
What are the drivin forces for the forward and reverse reactions?
Reverse:

tl<'l1f\ll''1

[,F'11'

[1<1 ~

Consider the following equilibrium system:

Forward:

LR1~

-Vii-

1.\~

t::

-VQ.

N'~Of>'1

Predict the effect that temperature change should have on this system and what should
be observed in response to the stress.
Increasing Temperature
Predicted response

'Bp-o'vJ

N tIC

Decreasing Temperature

Co IOVe.lLiC:

0l0UI1H,{~
8I2tll4N~R
Observed change
c)
Predict the effect that pressure change (by changing volume) should have on this
system an d w hats hou Id beo bserve d iIn response to t he stress.

Increasing pressure (Uvol)

Predicted response
Observed change

Decreasing pressure

1)(1 \1.t L fl

LlbH 71:. R

'\)AQI(~ ~

LI6H1(L

0 vol)

Or

I(

---t>

~()Jo..\~t,t

-----t:.

B"\- 0..

1..>_11\\

<;;;

'1 dQ.ffi

Mo.\:.e.

0:\

0.

'Il''rl

L\-"i\ibtivN\

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Q!~,'-.l\\'~~;'J""

(,N"'\\

ro.s.rQ~

nCl-tbQa.rfec..hJ

b'j

0.. c.<l.\a\'t~\

SCH4U: LeChatelier

and the Effect of Temperature

Changing the temperature will affect the rate of both the forward and the reverse reactions,
changing the value of the rate constant "k".
. The system will re-adjust the concentrations of reactants and products to settle into a new
equilibrium with a new Ke for the new temperature.
Consider the following system:
Forward Rxn: endothermic with Ea

= 125 kJ/mol

Reverse Rxn: exothermic with Ea = 75 kJ/mol

Ep
(k.l}

At equilibrium rate forward

rate reverse

When concentration of reactants/products are constant,

rate a "k" and "k" is dependent on temperature.
Rate a "k"

= Ae-Ea/RT

"k" a e-Ea/RT
Rxn

If this system is at equilibrium at 300 K, what will happen to the rate of each reaction if the
temperature is .Increase d to 3 15 K?
k

(Forward Rxn) at 300 K

KO(Q-r"'/l?T

ko<.

ENDOTHERMIC
k

\. c, +(,

RXN:

\(

0(

EXOTHERMIC

Q. -

kf(315K/kf(300K)

[10,'38
k

RXN:

(Reverse Rxn) at 315 K

\o../p-,

'6 ~I> I

Y Ie-'t.

krI315K/krI300K)

\ .%'1 15 )<, \ D~l\

\<.d-.

> \D-l'2-

(Reverse Rxn) at 300 K

\<D<.

(Forward Rxn) at 315 K

\<0( e. -t",1 FT

b(

(c. ""-

4.1 S

f2.-to../P-1

'3. bD?,

It

I D-)~

-2Increasing temperature will increase the rate of an endothermic rxn more than it increases the
rate of the exothermic rxn.
...Higher .T~mpfavours ENDOTHERMIC RXN
A similar analysis will show that decreasing temperature will slow down both reaction rates, but
the endothermic reaction will be affected to a greater degree.
Lower Temp favours the EXOTHERMIC RXN

SCH4U: LeChatelier and the Effect of Catalyst

Catalysts work by decreasing the activation energy of both forward and reverse rxns, Lets
assume that a catalyst for the previously studied rxn lowers the Ea by 25 kJ/mol.
(ie:
Ea forward (w/o cat) 125 kJ/mol
Ea forward (with
cat) 100 kJ/mol
Ea reverse(W/Ocat)= 75 kJ/mol
Ea reverse(Withcat)= 50 kJ/mol)

k (Forward Rxn) at 300 K (without catalyst)

1~\r:J...

_[o../ILO(

Forward rxn: kf(With

cat/kf(W/O
cat)=

(iX

-bo./g.,

rJ..

k (Reverse Rxn) at 300 K (with catalyst)

k~

12-

Reverse rxn: kr(With

call1kr(w/o
call=

e: f~/n

\O.~~

k (Reverse Rxn) at 300 K (without catalyst)

k (Forward Rxn) at 300 K (with catalyst)

-Co.!

QT

~.I~

The catalyst increases the rate of both forward and reverse reaction equally, as a result, it has
no effect on the equilibrium system.

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SCH4U: Equilibrium and LeChatelier's Principle

Although equilibrium prevents chemical reactions from reaching 100% yield, the
reaction still follows the stoichiometric mole ratio when it reacts. We can, therefore,
consider the amounts that react in terms of a quantity called "X".
1)

Consider the following chemical system:

N2(g) + 3H2(g) l'" 2NH3(g)
If we begin by adding 1 mole of N2 and 3 moles H2 to a closed 1 L reaction vessel, a
certain amount of each will react and a certain amount of NH3 will be produced before
the system reaches equilibrium.
If we call the amount of N? that reacts "X", then according to the mole ratio:
In terms of "X", what is the amount of H2 that must also react?

s".

In terms of "X", what is the amount of NH3 that must be produced?

Qx \'

Illustrate these changes by completing the following Concentration vs Time graph:

Concetration vs Time
rI~

T3
[mol/Ll

___

time

1'21<

The system above is now at equilibrium. According to LeChatelier's principle, what would
happen if at time "A" some NH~ is iniected into the system?

Illustrate these changes on the graph above.

-22)

Consider
Complete

the following
the following
.

equilibrium
system:
N204(g) '" 2N02(g) ~H +ve
concentration
vs time graph for this reaction .

, ..

.QQnce~trationvsTime

~I

)ime.
The system above is now at equilibrium.
happen to this svstem if the temperature

\0 t

=)

Fo.'J1:>\lt!':o

~C\h.,..H;'L

According to LeChatelier's
is increased at time "A"?
"r><1"\

f~rwo.",\

l \\\1.C\ l, 1 \, '( ) l NO,')

Illustrate

3)
a)

b)

c)

this effect

on the graph

l\-

fl"V')

a, .

above.

Consider the following equilibrium

Complete the following
concentration vs time
graph for this system.
If at time "A" NaCI(aq) is
added to the system,
illustrate the expected

~h:t~T~:
,~~~:m:\~

h'j

principle, what would

@6V6)

system:
{~&i1~entratIDrlvsTime

(CI~~
I

d)

Pb +(aq) is removed
from the system,
illustrate the expected
changes.
What would happen if at
time "C" more PbC12(s)
is added to the system?
t N/:) Crrcc.l}

SCH4U:
1)

Application

of LeChatelier's

Principle

For each of the given equilibria, state the system response to the applied stresses,
state how the concentration/amount
of each component will change as the new
equilibrium is reached.

and

A)
i)

Adding more CO2(g)

L
ii)

ll::>21 ~

Increasing
'1')(1"'-

-2

iii)

11'

(y)C(o.t03

pressure by decreasing

tor

\'\t,\)

.~"

the volume of container.

'Q,'I()\\r~~

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1~

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lc...",

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2S02(g) + 02(g)

i)

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[so31t
ii)

m 'CtO\()l~

J 't

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'" 2503(g)

b~ J",

[SD;t}t

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tD21"

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\1.\
-'f., iv)

Q..

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\JJ!.,) <. C!-

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No

~o

Lho..I)3Q.,

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ND Q.fF<ut. 1Iu.
D)

PCls(g)

i)

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ii)

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iii)

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iv)

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<;\/sLQ.f11

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fw\)

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vt .1~ It>Q.,1

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the volume.

'" Pb2+(aq) + 2CI1'(aq)

f~\j(J\J~'"

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I=\t\l

the pressure by adding helium gas to system

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'''f.: . iii)

to.. \ro

H'

C)

ii)

\1I\JouQ'i.

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b'f x .

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