Equilibrium

Chemistry 12 Unit 2 Notes - Equilibrium
Chemistry 12
Unit 2- Equilibrium
Notes
It's important to know that many chemical reactions are reversible. That is

Reactants Products or Reactants Products
Reactants form Products Products form Reactants
!or e"ample# un$er certain con$itions# one mole o% the colourless &as N
2
'
(
will decompose to
%orm two moles o% brown NO
2
gas
N
2
O
4
2 NO
2
colourless brown
Un$er other con$itions# you can take 2 moles o% brown N'
2
&as an$ chan&e it into one mole o%
N
2
'
(
&as
N
2
O
4
2 NO
2
colourless brown
In other wor$s# this reaction# as written may &o forward or in reverse, $epen$in& on the
con$itions.
I% we were to put some N
2
'
(
in a %lask# the N
2
'
(
molecules woul$ colli$e with each other an$
some o% them woul$ break apart to %orm N'
2
.
This process is in$icate$ by the forward reaction
N
2
O
4
2 NO
2
Unit 2 Notes Equilibrium Page 1
'nce this has happene$ %or awhile# there is a buil$ up o% N'
2
molecules in the same %lask
'nce in awhile# two N'
2
molecules will colli$e with each other an$ join to %orm a molecule o%
N
2
'
(
)
This process# as you mi&ht ha*e &uesse$ is in$icate$ by the reverse reaction:
N
2
O
4
2 NO
2
Two thin&s you'll ha*e to reali+e is that as long as there is N
2
O
4
present, the forward reaction
will keep on happening an$ as long as there is NO
2
present, the reverse reaction will keep
on happening!
,lso# you must keep in min$ that all these molecules are mi"e$ in the same container!
,t one particular time a molecule o% N
2
'
(
mi&ht be breakin& up# an$ at the same time two
molecules o% N'
2
mi&ht be -oinin& to %orm another molecule o% N
2
'
(
) .o here's an important
thin& to un$erstan$
In any reversible reaction, the forward reaction and the reverse reaction
are going on at the same time!
This is sometimes shown with a double arrow
N
2
O
4
2 NO
2

The double arrow means that
both the forward and reverse
reaction are happening at the
same time.
/ust a little comment here. The wor$ 0happening" has a similar meanin& to the wor$ 0 dynamic 0.
/ust remember that)
111111111111111111111111111111111111111111111111111
Now what we're &oin& to $o is look at how the rate o% the %orwar$ reaction chan&es i% we put
some pure N
2
'
(
in a %lask
I% we put some pure N
2
'
(
in a %lask 2No N'
2
yet)3# there will be a hi&h concentration o% N
2
'
(
.
That is# there will be lots o% N
2
'
(
molecules to colli$e with each other. .o at the be&innin& o%
our little e"periment# 2which we will call 0 time 0 4 03 the rate o% the forward reaction is quite fast.
N
2
O
4
2 NO
2
.o i% we were to make a graph o% the rate of the forward reaction *s. time# the &raph mi&ht start
out somethin& like this

10 9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
TIME (min)
RATE (forward)
'5# now you mi&ht ask 06hy $oes the rate o% the %orwar$ reaction &o down 7
6ell# i% you recall Unit 1# as the %orwar$ reaction procee$s
N
2
O
4
2 NO
2
the N
2
'
(
is use$ up an$ so it's concentration goes down. ,lso# you must remember that if the
concentration of a reactant goes down, there is less chances of collisions and the rate of the
reaction decreases.
,s the reaction continues# the slower rate will use up N
2
'
(
more slowly# so the 8N
2
'
(
9 will not
$ecrease so quickly an$ there%ore the rate will not $ecrease quite as quickly. 2:ea$ the last sentence
o*er a couple o% times an$ make sure it makes sense to you)3 !or those 0&raph wise0 people# you will
probably &uess that this means that the slope of the line on the &raph &ets more &ra$ual. The rest
o% the &raph mi&ht look somethin& like this

8 6 4 2 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
TIME (min)
RATE (forward)
N'6# it's time we consi$er the rate o% the reverse reaction.
,s you mi&ht recall# when we ha*e a container %ull o% pure N
2
'
(
# initially there is no N'
2
in
the container. .ince there is no N'
2
# there are no N'
2
molecules to colli$e with each other# an$
the rate of the reverse reaction is zero.
;ut o% course# as time &oes on# N'
2
is %orme$ %rom the forward reaction 2N
2
O
4
2 NO
2
3 so
in a short time# some N'
2
molecules can start colli$in& an$ the reverse reaction will be&in
2 N
2
O
4
2 NO
2
3
,s <':E N'
2
is %orme$ by the %orwar$ reaction# the rate of the reverse reaction graduall
increases. Now# %or you 0&raph bu%%s0# the &raph o% the Rate of the reverse reaction *s. Time
mi&ht look like this
10 9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
RATE (reverse)
TIME (min)
'5. Now# lets look at the &raph %or the %orwar$ rate and the re*erse rate to&ether

10 9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
RATE (forward)
RATE (reverse)
TIME (min)
N'6# %ocus your attention on the &raph at 0 Time = ( minutes 0 . >ou will notice that at this
point
the rate of the forward reaction ! the rate of the reverse reaction
,t this point# N'
2
is bein& use$ up at the same rate that it is bein& %orme$
N
2
O
4
2 NO
2
;ecause this is so# you shoul$ be able to con*ince yoursel% that the [NO
! is no longer
changing!
;ecause the re*erse rate is equal to the %orwar$ rate# N
2
'
(
is bein& %orme$ at the same rate it is
bein& use$ up. .o# also the "N
2
O
4
# is no longer changing either!
Can you pre$ict what will happen to the &raph a%ter (.4 minutes7
>'U ?UE..E@ IT) The rates o% the %orwar$ reaction an$ the re*erse reaction# no lon&er chan&e
because the "N
2
O
4
# is constant an$ the"NO
2
# is also constant. The &raph will look like this

12 10 8 6 4 2 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
RATE (forward)
RATE (reverse)
TIME (min)
The situation happenin& %rom (.4 minutes on in this &raph has a special name an$ a special
si&ni%icance. ,t this point# the system 2meanin& the container# the N
2
'
(
an$ the N'
2
3 is sai$ to
be at e$uilibrium. To $escribe it e*en more precisely# we can say that we have reached a state
of dnamic e$uilibrium..
Aere are some thin&s that you must "nderstand about dnamic e$uilibrium
1. The reaction has not stopped!
2. The %orwar$ an$ the re*erse reaction continue to ta#e place# but their rates are e$"al
so there are no chan&es in concentrations o% reactants or pro$ucts. 2The %orwar$ an$
re*erse reactions are sai$ to be 0 balance$ 03 e&. %or the reaction
N
2
O
4
2 NO
2
%or each N
2
'
(
molecule that breaks up to %orm two N'
2
molecules# two other N'
2

molecules combine to %orm another N
2
'
(
molecule. ,ll this is happenin& on the
microscopic level# so we $on't see in$i*i$ual molecules reactin&.
B. ,s %ar as we can see %rom the 0outsi$e0# there appears to be nothin& happenin&. ,ll
observable properties are constant. These inclu$e the concentrations o% all reactants
an$ pro$ucts# the total pressure# colour# temperature etc.
(. I% no chan&es were ma$e in con$itions an$ nothin& is a$$e$ or taken away# a
system at equilibrium woul$ remain that way %ore*er# the %orwar$ an$ re*erse
reactions 0tickin& away0# but balance$ so that no obser*able chan&es happen.
Aere are a couple o% other thin&s to consi$er be%ore we summari+e e*erythin&
1. Chan&in& the temperature can alter the rates o% the reactions at equilibrium. This coul$
0throw o%%0 the balance. .o# for a sstem at e$uilibrium, the temperature must
remain constant and uniform throughout the sstem.
2. Cettin& material into or out o% the system will a%%ect rates so a sstem at e$uilibrium
is a closed sstem.
B. ,&ain# consi$er the equilibrium reaction N
2
O
4
2 NO
2

In the e"ample that we $i$ to construct the &raphs# we ha$ starte$ with p"re N
O
%

an$ no N'
2
. The %orwar$ reaction rate was hi&h at the start# but the re*erse reaction
rate e*entually 0cau&ht up0# the rates became equal an$ e$uilibrium was establishe$.
Can you &uess what woul$ happen i% we ha$ starte$ with p"re NO
instea$
2no N
2
'
(
37 The re*erse rate woul$ start out hi&h an$ the %orwar$ rate# +ero. In time#
the %orwar$ rate woul$ 0 catch up 0. 6hen the rates became e$"al# a&ain e$uilibrium
woul$ be establishe$.
6e can summari+e all this by sayin& that the e$uilibrium can be approached from
the left %starting with reactants& or from the right %starting with products&
/ust a little term be%ore we summari+e The wor$ macroscopic means large scale or visible or
observable. 2The opposite is microscopic# which means too small to see e&. molecular le*el3.
.ome macroscopic properties are total pressure# colour# concentrations# temperature# $ensity etc.
,lri&ht# let's summari+e
'haracteristics of a (stem at )namic *$uilibrium
1. The rate o% the forward reaction = The rate o% the reverse reaction
2. +icroscopic processes 2the %orwar$ an$ re*erse reaction3 continue in a balance
which yiel$s no macroscopic changes. 2so nothin& appears to be happenin&.3
B. The system is closed an$ the temperature is constant an$ uniform throu&hout.
(. The equilibrium can be approache$ %rom the left 2startin& with reactants3 or %rom the
right 2startin& with prod"cts3.
*nthalp
Enthalpy is 0 The heat content of a system. 0 ,nother way to think o% enthalpy is as 0&hemical
'otential (nergy0.
,ny chan&e in the Dotential Ener&y o% a system means the same thin& as the 0 Enthalpy Chan&e 0. The
symbol %or Enthalpy is 0 A 0. There%ore the 0chan&e in Enthalpy0 o% a chemical reaction is calle$
0H0. In Chemistry 12# a Dotential Ener&y @ia&ram is the same thin& as an 0Enthalpy @ia&ram

Enthalpy
H
Progress of Reaction
The "Entha!"
#han$e"
Rea%tants
&rod'%ts
The rea%t(on shown on th(s $ra!h (s E)other*(%. Th(s *eans that heat (s
reeased or $(ven o+. ,hat was $(ven o+ as heat ener$" was ost as
Entha!" fro* the rea%tants. The net ener$" %han$e -etween the
!rod'%ts and the rea%tants (s %aed the Entha!" #han$e ( .). As "o' %an
see/ the entha!" %han$e (.) (n th(s rea%t(on (s negative. (Th(s (s awa"s
the %ase when the &rod'%ts are ower on the &otent(a Ener$" (Entha!")
0ra!h.)
An exothermic rea%t(on
In an *,othermic Reaction )* is negative+, the *nthalp is decreasing.
In an *ndothermic Reaction )* is positive+, the *nthalp is increasin&.
I% the 0*eat Term0 is written right in the e$"ation. 2a 0thermochemical equation0.3
I% the heat term is on the left si$e# it means heat is bein& "sed "p an$ it's endothermic.
I% the heat term is on the right si$e# heat is bein& released an$ it's e,othermic.
Cook at the %ollowin& e"amples
1. , E ; C E @ A = -2( k/ is e,othermic so enthalpy is decreasing.

2. F E > G A = HI k/ is endothermic so enthalpy is increasing.
B. E E @ ! E (J k/ is e,othermic so enthalpy is decreasing.
(. ? E / E BK k/ C E < is endothermic so enthalpy is increasing.
.ystems will ten$ towar$ a state o% lower potential energ i% nothin& else is actin& upon them.
In Chemistry# we are intereste$ in is chemical potential energy# otherwise known as enthalp)
'hemical sstems will tend toward a state of minimum enthalp if sufficient
activation energ is available and no other factors are considered.
,nother way o% statin& this mi&ht be
- chemical reaction will favour the side %reactants or products& with
minimum enthalp if no other factors are considered.
Thus %or an e,othermic reaction# i% no other %actors are consi$ere$
Enthalpy
H
The "Entha!"
#han$e"
Rea%tants
&rod'%ts
An exothermic rea%t(on
Here, the Products have lower enthalpythan the Reactants so the reaction tends to
"favour the products". In other words, if the reactants are mixed, they will tend to
form products spontaneously (without outside assistance) rather than remain as
reactants.
The products will be favoured because the pro$ucts ha*e minimum enthalp. In other wor$s# there is
a natural ten$ency here %or reactants to spontaneously %orm pro$ucts.
In an endothermic reaction# the LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL ha*e minimum
enthalpy# so the LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL will be %a*oure$. In other wor$s# i%
the reactants are mi"e$ they will 2ten$ to remain as reactants M spontaneously %orm pro$ucts3 LLLLLLLLLLLLLL

Cet's look at a $ia&ram %or an endothermic reaction-
. (s !os(t(ve
An endothermi% rea%t(on
Rea%tants
&rod'%ts
Enthalpy
In the case of an endothermicreaction, the enthalpy of the Reactantsis lower than the
enthalpy of the Products. Since chemical systems favour a state of minimum enthalpy,
the Reactants are favouredin this case. In other words if the reactants are mixed, they
will tend to remain as reactants rather than forming products.
11111111111111111111111111111111111111111111111111
1. Tell whether each o% the %ollowin& is endothermic or e,othermic an$ state which has minimum
enthalp, the reactants or the prod"cts
a. DCl
J2&3
Cl
22&3
E DCl
B2&3
A = N2.J k/
LLLLLLLLLLthermic an$ the LLLLLLLLLLLLLLLLLLL ha*e minim"m enthalpy.
b 2NA
B2&3
E N2.( k/

N
22&3
E BA
22&3
c C'
2&3
E BA
22&3
CA
(2&3
E A
2
'
2&3
E (N.B k/
$. Cl
22&3
Cl
22aq3
A = -2J k/
2. 6hen no other %actors are consi$ere$# a reaction will mo*e in such a way 2le%t or ri&ht3 in
or$er to achie*e a state o% LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL enthalpy.
B ?i*en the equation 2NA
B2&3
E N2.( k/

N
22&3
E BA
22&3
I% only the enthalpy is consi$ere$# the 2reactant M pro$ucts3 LLLLLLLLLLLLLLLLLLLLLLLLLLLL
will be %a*oure$ at equilibrium.
(. ?i*en the equation Cl
22&3
Cl
22aq3
A = -2J k/
I% only the enthalpy is consi$ere$# the 2reactant M pro$ucts3 LLLLLLLLLLLLLLLLLLLLLLLLLLLL
will be %a*oure$ at equilibrium.
J I% the reaction C'
2&3
E BA
22&3
CA
(2&3
E A
2
'
2&3
E (N.B k/
was procee$in& to the right# the enthalpy woul$ be LLLLLLLLLLLLLLLLLLLLLin&. Is this a
favo"rable chan&e7 LLLLLLLLLLLLL.
K. I% the reaction DCl
J2&3
Cl
22&3
E DCl
B2&3
A = N2.J k/
was procee$in& to the right# the enthalpy woul$ be LLLLLLLLLLLLLLLLLLLLin&. Is this a
I. I% the reaction Cl
22&3
Cl
22aq3
A = -2J k/
H I% the reaction 2NA
B2&3
E N2.( k/

N
22&3
E BA
22&3
,s you can see by lookin& at the e"ercises abo*e# there are two ways o% lookin& at what happens to the
enthalpy
.f the reaction is e,othermic, the products have minimum enthalp and the
formation of products %move toward the right& is favourable.
.f the reaction is endothermic, the reactants have minimum enthalp and
the formation of products %move toward the right& is unfavourable. .n
this case the formation of reactants %move toward the left& is favourable.

1111111111111111111111111111111111111111111111111111111
Now# consi$er the simple melting o% water
/
2
O
%s&
0 1 heat

/
2
O
%l&
2the subscript
2s3
stan$s %or solid3 2the subscript
2l3
stan$s %or li$"id3
I% we were to look at only the enthalpy in this process# you can see that the reactant 2 /
2
O
%s&
3 woul$
ha*e minimum enthalpy an$ woul$ be %a*oure$. .o all of the water in the "niverse sho"ld e,ist only
as a solid! 2It woul$ not be %a*ourable %or water to e"ist as a liqui$)3 6e woul$ all be %ro+en soli$))))
The answer to this problem lies in lookin& at another factor that &o*erns equilibrium. That %actor is
calle$ entrop 2or randomness or disorder3
1111111111111111111111111111111111111111111111111111111
*ntrop
*ntrop simpl means disorder, or lack of order.
In ?ra$e H# you probably learne$ about the arran&ement o% molecules in soli$s# liqui$s an$ &ases.
The particles in a solid are
very close together and very
ordered . A solid has very
low entropy .
(very little disorder)
The particles in a liquidare fairly close
together and they are not as ordered as
they are in the solid. A liquid has higher
entropy than a solid , but less entropy
than a gas .
The particles of a gas are very far apart
and they are moving randomly (all
different directions - any old way!).
They have very little order. A gas has
very high entropy .
.o we can summari+e by sayin& that
*ntrop of a (olid 2 *ntrop of a 3i$uid 2 *ntrop of a 4as
6e can look at a chemical equation with subscripts showin& the phases an$ tell which has ma,imum
entrop# the reactants or the prod"cts.
In other wor$s# they can look at an equation an$ tell whether entrop is increasing or decreasing as
the reaction proceeds to the right.
In the %ollowin& e"amples# the entrop is increasing 2or the products ha*e greater entrop3
1. There is a gas 2or &ases3 on the right# when there are no gases on the left o% the
equation
CaC'
B2s3
E O 2 ACl
2aq3

CaCl
22aq3
E CO
2(g)
E A
2
'
2l3

a &as is %orme$ on the ri&ht.
2. 6hen there are gases on both sides# the products ha*e greater entrop when there
are more moles of gas on the right 2a$$ up coe%%icients o% &ases on le%t an$ ri&ht.3
(NA
B2&3
E J'
22&3

(N'
2&3
O E KA
2
'
2&3


There are (4 + 5) = 9 moles of
gas on the left

There are (4 + 6) = 10 moles of
gas on the right.
,nother way to look at the last e"ample is to say that
5 6he side with the greater number of moles of gas has the greatest entrop. 5
B. 6hen a solid dissolves in water# the products 2 the aqueous solution o% ions 3 ha*e
greater entrop. This makes sense because
+ -
+ -
-
-
-
+
+
-
-
+
+
+
+
-
O
H
H
O
H
H
O
H
H
O
H
H
+
O
H
H
O
H
H
O
H
H
O
H
H
- O
H
H
O
H
H
O
H
H
O
H
H
+
O
H
H
O
H
H
O
H
H
O
H
H
-
SOLID
Dissolving
An Aqueous Solution
The ions in a Solid are
very ordered. They have
low entropy .
When dissolved in water, the ions are separatedand
surrounded by water molecules . The ions are much more
spread outand disordered . The entropy of an aqueous
solution is higher than that of a solid .
So in order of lowest to highest entropy:
Solids < Liquids < Aqueous solutions < Gases < More moles of Gas
Aere are %ew e"ercises %or you
N. !or each o% the %ollowin&# $eci$e whether the reactants or the products ha*e greater
entrop
a3 I
22s3
I
22aq3
The LLLLLLLLLLLLLLLLLLLLLLLL ha*e &reater entropy.
b3 2NA
B2&3
N
22&3
E BA
22&3
The LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLha*e &reater entropy.
c3 NA
B2&3
NA
B2aq3
The LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLha*e &reater entropy.
$3 C'
2&3
E Cl
22&3
C'Cl
22&3

e3 <&C'
B2s3
E 2ACl
2aq3
<&Cl
22aq3
E A
2
'
2l3
E C'
22&3

I% you ha*e any questions about these# check with your teacher)
11111111111111111111111111111111111111111111111

:emember /
2
O
%s&
01 heat

/
2
O
%l&

6e $eci$e$ that all the A
2
' in the uni*erse shoul$ remain as a solid because /
2
O
%s&
has lower
enthalp than /
2
O
%l&
an$ nature favours a state of minimum enthalp.
6ell# now we can e"plain why there is some liqui$ water in the uni*erse 2lots o% it3
/
2
O
%l&
has higher entrop than /
2
O
%s&
There is a natural ten$ency in nature towar$ ma,im"m disorder or ma,imum entrop)
'hemical sstems will tend toward a state of ma,imum entrop if no other factors are
considered.
,nother was o% statin& this mi&ht be
ma,imum entrop if no other factors are considered.
:emember# the other %actor which controlle$ reactions was enthalp. 2chemical potential ener&y3.
,lso remember that
'hemical sstems will tend toward a state of minimum enthalp if sufficient
activation energ is available and no other factors are considered.
or
minimum enthalp if no other factors are considered.
>ou %i&ure out which has the most enthalp 2reactants or pro$ucts3 by lookin& at the A or the heat
term.
,lso# remember that you can %i&ure out which has the more entrop 2reactants or pro$ucts3 by lookin&
at the subscripts which represent the phases.
,lso# we can combine the rules about 0natural ten$encies0 to come up with this
In nat"re, there is a tendency toward minimum enthalp and ma,imum entrop.
Now# let's consi$er this process a&ain
/
2
O
%s&
0 1 heat

/
2
O
%l&

The two ten$encies are sai$ to 0oppose each other0 in this case
The ten$ency towar$ minimum enthalp woul$ favour the reactant )2 since you ha*e to a$$ heat
ener&y to /
2
O
%s&
to &et /
2
O
%l&
# /
2
O
%s&
has minimum enthalp3
In this case the ten$ency towar$ ma,imum entrop woul$ ten$ to favour the product. 2, li$"id has
more entropy 2$isor$er3 than a solid3
6e say that
6hen the two ten$encies oppose each other 2one %a*ours reactants# the other %a*ours
pro$ucts3# the reaction will reach a state of e$uilibrium.
That is, there will be some reactants and some prod"cts present. The relative amo"nts of
each depends on conditions li#e temperat"re, press"re, concentration etc.
.ince this is the case with /
2
O
%s&
0 1 heat

/
2
O
%l&
# there is some soli$ water an$ some liqui$
water in the uni*erse. 2In other wor$s# there is a state o% equilibrium3 6hich one is present in the
&reater amount is $etermine$ lar&ely by the temperature.
11111111111111111111111111111111111111111111111
Now# lets consi$er another simple process , &lass bottle is knocke$ $own %rom a hi&h shel% onto a
concrete %loor an$ the &lass shatters
7ottle on a high shelf 6housands of pieces of glass on a concrete floor
The bottle %alls down an$ not up) This happens because there is a natural ten$ency towar$ minimum
gravitational potential energ 2like minimum enthalp in chemistry3
In other wor$s the ten$ency towar$ minimum gravitational potential energ %a*ours the
products 2the low bottle rather than the hi&h3
2The person who knocke$ the bottle o%% o% the shel% was simply supplyin& the 0 acti*ation ener&y 03
:emember that the bottle broke into thousan$s o% pieces when it hit the concrete. The broken pieces o%
&lass ha*e more disorder 2entrop3 than the bottle# so in this process# the ten$ency towar$ ma,imum
entrop also favours the products)
Bottle on a high shelf Thousands of pieces of glass on a concrete floor
Products have
minimum "enthalpy" ,
so the tendency
toward minimum
enthalpy favours the
products .
Products have
maximum entropy, so
the tendency toward
maximum entropy
favours the products .
There is no 0equilibrium0 here when the process is %inishe$. That bottle has completely %allen $own
an$ it is all broken. 2This bottle is no lon&er on the shel% an$ it is no lon&er an 0unbroken bottle03
6e can summari+e what happene$ here
Drocesses in which both the ten$ency towar$ minimum enthalp an$ towar$
ma,imum entrop %a*our the products# will go to completion.
2ie. ,ll reactants will be con*erte$ into pro$ucts. There will be no reactants le%t once the
process is %inishe$)3
Aere's an e"ample o% a chemical reaction in which this happens
28
%s&
1 2/
2
O
%l&
28O/
%a$&
1 /
2%g&
1 heat
This process is e,othermic 2the heat term is on the ri&ht3 so the prod"cts have lower enthalpy.
The ten$ency towar$ minimum enthalp %a*ours the products.
There is a mole o% &as on the ri&ht 2/
2%g&
3 an$ no &ases in the reactantsP There%ore# the prod"cts ha*e
greater entropy.
The ten$ency towar$ ma,imum entrop %a*ours the products.
.ince both tendencies favour the products# this reaction will go to completion.
That is# all o% the reactants 2assumin& you ha*e the correct mole ratios e&. 2 moles o% 5 to 2 moles o%
A
2
'3 will be con*erte$ to pro$ucts.
I% one reactant is in e,cess# the limiting reactant will be completely cons"med.
.o# i% you put a little bit o% potassium in a beaker o% water# the reaction will keep &oin& until all o% the
potassium is use$ up. There will be no potassium le%t once the reaction is complete.
In other wor$s# the re*erse reaction $oes not occur)
11111111111111111111111111111111111111111111111
Cet's consi$er one more process
28O/
%a$&
1 /
2%g&
1 heat 28
%s&
1 2/
2
O
%l&
In this case# the tendency toward minimum enthalp favo"rs the reactants# an$ the
tendency toward ma,imum entrop also favo"rs the reactants.
Drocesses in which both the ten$ency towar$ minimum enthalp an$ towar$
ma,imum entrop %a*our the reactants# will not occur at all!.
2ie. None o% the reactants will be con*erte$ into pro$ucts. There will be no pro$ucts
%orme$)3
NO6*: This woul$ be like thousan$s o% pieces o% &lass spontaneously stickin& to&ether# %ormin& a
bottle an$ -umpin& up onto a hi&h shel%) This $oes not occur at all. 2,t least I'*e ne*er seen it happen)3
11111111111111111111111111111111111111111111111
To summari+e
6hen the two ten$encies oppose each other 2one %a*ours reactants# the other %a*ours
pro$ucts3# the reaction will reach a state of e$uilibrium.
Drocesses in which both the ten$ency towar$ minimum enthalp an$ towar$ ma,imum
entrop %a*our the products# will go to completion.
Drocesses in which both the ten$ency towar$ minimum enthalp an$ towar$ ma,imum
entrop %a*our the reactants# will not occur at all!.
11111111111111111111111111111111111111111111111
14. !or each o% the %ollowin& reactions $eci$e which has minimum enthalp 2reactants or pro$ucts3#
which has ma,imum entrop 2reactants or pro$ucts3# an$ i% the reactants are mi"e$# what will
happen7 2&o to completionM reach a state o% equilibriumMnot occur at all3.
a3 DCl
B2&3
E Cl
22&3
DCl
J2&3
Q A = -N2.J k/
The LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL hasMha*e minimum enthalpy.
The LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL hasMha*e ma"imum entropy.
I% DCl
B
an$ Cl
2
are put to&ether# what shoul$ happen72&o to completionM reach a state o%
equilibriumMnot occur at all3
LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
b3 2N'
22&3

N
2
'
(2&3
E ener&y
I% N'
2
was put in a %lask# what shoul$ happen72&o to completionM reach a state o%
LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
c3 D(
2s3
E KA
22&3
E BI k/

(DA
B2&3

I% D
(2s3
an$ KA
22&3
$3 2Db'
2s3
E (N'
22&3
E '
22&3

2Db2N'
B
3
22s3
Q A = - JNI k/
The LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL hasMha*e ma"imum entropy.
I% Db'
2s3
an$ N'
22&3
were put in a %lask# what shoul$ happen72&o to completionM reach a state
o% equilibriumMnot occur at all3
More Questions:
1. 6hat is meant by enthalp9 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
2. 6hat is meant by entrop9 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
B. In an endothermic reaction# the LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL ha*e
minimum enthalp.
(. In an e,othermic reaction# the LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL ha*e
minimum enthalp.
J. ,rran&e the %ollowin& in or$er %rom least entrop to greatest entrop
a3 liqui$s b3 &ases c3 aqueous solutions $3 soli$s
LLLLLLLLLLLLL R LLLLLLLLLLLLL R LLLLLLLLLLLLL R LLLLLLLLLLLLL
K. There is a natural ten$ency towar$ LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLenthalp
an$ LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL entrop.
I. , process in which entrop increases an$ enthalp decreases will
2&o to completionM reach a state o% equilibriumMnot occur at all3 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
H. , process in which entrop increases an$ enthalp increases will
N. , process in which entrop decreases an$ enthalp decreases will
14. , process in which entrop decreases an$ enthalp increases will
11. , process in which both the enthalp and entrop trends favour reactants will

12. , process in which both the enthalp and entrop trends favour products will

1B. , process in which the enthalp and entrop trends oppose each other will

1(. In each o% the %ollowin&# state which has the ma,imum entrop# 2reactants or pro$ucts3
a3 C
2s3
O E '
22&3

C'
22&3
LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
b3 2,l2s3 E KACl
2aq3

BA
22&3
EO 2,lCl
B2aq3 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
c3 2.'
B2&3
2.'
22&3
O E '
22&3
LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
$3 ACl
2&3

A
E
2aq3
EO Cl
-
2aq3
LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
e3 5'A
2s3

5
E
2aq3
+

O 'A
-
2aq3
LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
1J. !or each o% the %ollowin& reactions $eci$e which has minimum enthalp 2reactants or pro$ucts3#
which has ma,imum entrop 2reactants or pro$ucts3# an$ i% the reactants are mi"e$# what will
happen7 2&o to completionM reach a state o% equilibriumMnot occur at all3. ,ssume there is su%%icient
acti*ation ener&y to initiate any spontaneous reaction.
a3 DCl
J2&3

DCl
B2&3
E Cl
22&3
Q A = EN2.J k/
The LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL hasMha*ema"imum entropy.
I% DCl
J
is put in a %lask what shoul$ happen72&o to completionM reach a state o%
LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
b3 2N'
2&3
E '
22&3
2N'
22&3
E ener&y
I% N'

an$ '
2
were put in a %lask# what shoul$ happen72&o to completionM reach a state o%
c3 Na
2
C'
B2s3
E 2ACl
2aq3

2NaCl
2aq3
E C'
22&3
E A
2
'
2l3
E 2I.I k/
I% Na
2
C'
B2s3
OE 2ACl
2aq3
were put in a %lask# what shoul$ happen72&o to completionM
reach a state o% equilibriumMnot occur at all3
$3 2Db2N'
B
3
22s3
E JNI k/

2Db'
2s3
E (N'
22&3
E '
22&3
Q
I% Db2N'
B
3
2
1K. :eactions which result in aMan LLLLLLLLLLLLLLLLLLLLLLLLLLLLLL in enthalpy an$ aMan
LLLLLLLLLLLLLLLLLLLLLLLLLLLLL in entropy will alwas be spontaneous.
1I. :eactions which result in aMan LLLLLLLLLLLLLLLLLLLLLLLLLLLLLL in enthalpy an$ aMan
LLLLLLLLLLLLLLLLLLLLLLLLLLLLLL in entropy will alwas be non-spontaneous.
Do or!s"eet 2-#

Equilibrium

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Equilibrium

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Chemistry 12 Unit 2 Notes - Equilibrium

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