Ncert ch6 Chemistry Class 11
Ncert ch6 Chemistry Class 11
154 CHEMISTRY
UNIT 6
THERMODYNAMICS
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
155
THERMODYNAMICS 155
* We could have chosen only the reactants as system then walls of the beakers will act as boundary.
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
156
156 CHEMISTRY
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
157
THERMODYNAMICS 157
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
158
158 CHEMISTRY
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
159
THERMODYNAMICS 159
be achieved in a single step and the final If the pressure is not constant but changes
volume be Vf . During this compression, during the process such that it is always
suppose piston moves a distance, l and is infinitesimally greater than the pressure of the
cross-sectional area of the piston is A gas, then, at each stage of compression, the
[Fig. 6.5(a)]. volume decreases by an infinitesimal amount,
then, volume change = l × A = ΔV = (Vf – Vi ) dV. In such a case we can calculate the work
done on the gas by the relation
for
We also know, pressure = Vf
ar
w =− ∫p ex dV ( 6.3)
Therefore, force on the piston = pex . A Vi
If w is the work done on the system by Here, pex at each stage is equal to (pin + dp) in
movement of the piston then case of compression [Fig. 6.5(c)]. In an
w = force × distance = pex . A .l expansion process under similar conditions,
= pex . (–ΔV) = – pex ΔV = – pex (Vf – Vi ) (6.2) the external pressure is always less than the
pressure of the system i.e., pex = (pin– dp). In
The negative sign of this expression is general case we can write, pex = (pin + dp). Such
required to obtain conventional sign for w, processes are called reversible processes.
which will be positive. It indicates that in case A process or change is said to be
of compression work is done on the system. reversible, if a change is brought out in
Here (Vf – Vi ) will be negative and negative such a way that the process could, at any
multiplied by negative will be positive. Hence moment, be reversed by an infinitesimal
the sign obtained for the work will be positive. change. A reversible process proceeds
If the pressure is not constant at every infinitely slowly by a series of equilibrium
stage of compression, but changes in number states such that system and the
of finite steps, work done on the gas will be surroundings are always in near
summed over all the steps and will be equal equilibrium with each other. Processes
to − ∑ p ΔV [Fig. 6.5 (b)]
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
160
160 CHEMISTRY
other than reversible processes are known Isothermal and free expansion of an
as irreversible processes. ideal gas
In chemistry, we face problems that can For isothermal (T = constant) expansion of an
be solved if we relate the work term to the ideal gas into vacuum ; w = 0 since pex = 0.
internal pressure of the system. We can Also, Joule determined experimentally that
relate work to internal pressure of the system q = 0; therefore, ΔU = 0
under reversible conditions by writing Equation 6.1, Δ U = q + w can be
equation 6.3 as follows: expressed for isothermal irreversible and
Vf
reversible changes as follows:
w rev = − ∫p ex d 1. For isothermal irreversible change
Vi q = – w = pex (Vf – Vi )
Since dp × dV is very small we can write 2. For isothermal reversible change
Vf Vf
w rev = − ∫ pin dV (6.4) q = – w = nRT ln V
i
Vi
Vf
Now, the pressure of the gas (pin which we = 2.303 nRT log
Vi
can write as p now) can be expressed in terms
of its volume through gas equation. For n mol 3. For adiabatic change, q = 0,
of an ideal gas i.e., pV =nRT ΔU = wad
nRT
⇒p = Problem 6.2
V
Therefore, at constant temperature (isothermal Two litres of an ideal gas at a pressure of
process), 10 atm expands isothermally into a
Vf
vacuum until its total volume is 10 litres.
How much heat is absorbed and how
w rev = − ∫ nRT
much work is done in the expansion ?
Vi
Solution
Vf
= – 2.303 nRT log (6.5) We have q = – w = pex (10 – 2) = 0(8) = 0
Vi
No work is done; no heat is absorbed.
Free expansion: Expansion of a gas in
Problem 6.3
vacuum (pex = 0) is called free expansion. No
work is done during free expansion of an ideal Consider the same expansion, but this
gas whether the process is reversible or time against a constant external pressure
irreversible (equation 6.2 and 6.3). of 1 atm.
Now, we can write equation 6.1 in number Solution
of ways depending on the type of processes. We have q = – w = pex (8) = 8 litre-atm
Let us substitute w = – pexΔV (eq. 6.2) in Problem 6.4
equation 6.1, and we get Consider the same expansion, to a final
volume of 10 litres conducted reversibly.
ΔU = q − pex ΔV
Solution
If a process is carried out at constant volume
(ΔV = 0), then 10
We have q = – w = 2.303 × 10 log
ΔU = qV 2
the subscript V in qV denotes that heat is = 16.1 litre-atm
supplied at constant volume.
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
161
THERMODYNAMICS 161
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
162
162 CHEMISTRY
Solution halved, each part [Fig. 6.6 (b)] now has one
V
(i) The change H2O (l ) → H2
half of the original volume, , but the
2
temperature will still remain the same i.e., T.
ΔH = ΔU + Δn It is clear that volume is an extensive property
and temperature is an intensive property.
or ΔU = ΔH – Δn g RT , substituting the
values, we get
ΔU = 41.00 kJ
× 8.3 J
= 41.00 kJ m
= 37.904 kJ mol–1 Fig. 6.6(a) A gas at volume V and temperature T
(ii) The change H2 O (l ) → H2 O
There is negligible change in volume,
So, we can put p ΔV = Δn g RT in this
case,
ΔH ≅ ΔU
so, ΔU = 41. Fig. 6.6 (b) Partition, each part having half the
volume of the gas
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
163
THERMODYNAMICS 163
one mole of the substance and is the quantity heat capacity of the liquid in which calorimeter
of heat needed to raise the temperature of one is immersed and the heat capacity of
mole by one degree celsius (or one kelvin). calorimeter, it is possible to determine the heat
Specific heat, also called specific heat capacity evolved in the process by measuring
is the quantity of heat required to raise the temperature changes. Measurements are
temperature of one unit mass of a substance made under two different conditions:
by one degree celsius (or one kelvin). For i) at constant volume, qV
finding out the heat, q, required to raise the
ii) at constant pressure, qp
temperatures of a sample, we multiply the
specific heat of the substance, c, by the mass (a) ΔU measurements
m, and temperatures change, ΔT as For chemical reactions, heat absorbed at
constant volume, is measured in a bomb
q = c × m × ΔT (6.11)
calorimeter (Fig. 6.7). Here, a steel vessel (the
(d) The relationship between Cp and CV for bomb) is immersed in a water bath. The whole
an ideal gas device is called calorimeter. The steel vessel is
At constant volume, the heat capacity, C is immersed in water bath to ensure that no heat
denoted by CV and at constant pressure, this is lost to the surroundings. A combustible
is denoted by Cp . Let us find the relationship substance is burnt in pure dioxygen supplied
between the two. in the steel bomb. Heat evolved during the
reaction is transferred to the water around the
We can write equation for heat, q
bomb and its temperature is monitored. Since
at constant volume as qV = CV ΔT = ΔU the bomb calorimeter is sealed, its volume does
not change i.e., the energy changes associated
at constant pressure as qp = C p ΔT = ΔH with reactions are measured at constant
The difference between Cp and CV can be volume. Under these conditions, no work is
derived for an ideal gas as:
For a mole of an ideal gas, ΔH = ΔU + Δ(pV )
= ΔU + Δ(RT )
= ΔU + RΔT
∴ ΔH = ΔU + R (6.12)
On putting the values of ΔH and ΔU,
we have
C p ΔT = CV ΔT
C p = CV + R
C p − CV = R (6.13)
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
164
164 CHEMISTRY
12.0 g mol −1
=
1
= – 2.48 ×102 kJ mol–1
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
165
THERMODYNAMICS 165
Δr H = (sum of enthalpies of products) – (sum melting. Normally this melting takes place at
of enthalpies of reactants) constant pressure (atmospheric pressure) and
during phase change, temperature remains
= ∑ a i H products (6.14) constant (at 273 K).
i
H2O(s) → H2O
(Here symbol ∑ (sigma) is used for
summation and ai and bi are the stoichiometric Here ΔfusH 0 is enthalpy of fusion in standard
coefficients of the products and reactants state. If water freezes, then process is reversed
respectively in the balanced chemical and equal amount of heat is given off to the
equation. For example, for the reaction surroundings.
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) The enthalpy change that accompanies
melting of one mole of a solid substance
Δr H = ∑ a i H p in standard state is called standard
i
enthalpy of fusion or molar enthalpy of
= [Hm (CO2 ,g) + 2Hm (H2O, l)]– [Hm (CH4 , g) fusion, ΔfusH 0.
+ 2Hm (O2, g)] Melting of a solid is endothermic, so all
where Hm is the molar enthalpy. enthalpies of fusion are positive. Water requires
Enthalpy change is a very useful quantity. heat for evaporation. At constant temperature
Knowledge of this quantity is required when of its boiling point Tb and at constant pressure:
one needs to plan the heating or cooling H 2 O(l) → H 2 O
required to maintain an industrial chemical
reaction at constant temperature. It is also ΔvapH 0 is the standard enthalpy of vaporization.
required to calculate temperature dependence
Amount of heat required to vaporize
of equilibrium constant.
one mole of a liquid at constant
(a) Standard enthalpy of reactions temperature and under standard pressure
Enthalpy of a reaction depends on the (1bar) is called its standard enthalpy of
conditions under which a reaction is carried vaporization or molar enthalpy of
out. It is, therefore, necessary that we must vaporization, ΔvapH .
0
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
166
166 CHEMISTRY
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
167
THERMODYNAMICS 167
Δf H ) at 298K of a
Table 6.2 Standard Molar Enthalpies of Formation (Δ
Few Selected Substances
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
168
168 CHEMISTRY
enthalpy of formation of HBr (g) is written as (alongwith allotropic state) of the substance in
an equation. For example:
½H 2 (g) + ½Br2
C2 H5 OH(l ) + 3
Standard enthalpies of formation of some
common substances are given in Table 6.2. The above equation describes the
By convention, standard enthalpy for combustion of liquid ethanol at constant
formation, Δf H 0, of an element in reference temperature and pressure. The negative sign
state, i.e., its most stable state of aggregation of enthalpy change indicates that this is an
is taken as zero. exothermic reaction.
Suppose, you are a chemical engineer and It would be necessary to remember the
want to know how much heat is required to following conventions regarding thermo-
decompose calcium carbonate to lime and chemical equations.
carbon dioxide, with all the substances in their
standard state. 1. The coefficients in a balanced thermo-
chemical equation refer to the number of
CaCO3 (s) → C moles (never molecules) of reactants and
Here, we can make use of standard enthalpy products involved in the reaction.
2. The numerical value of ΔrH refers to the
0
of formation and calculate the enthalpy
change for the reaction. The following general number of moles of substances specified
equation can be used for the enthalpy change by an equation. Standard enthalpy change
calculation. ΔrH 0 will have units as kJ mol–1.
Δr H V = ∑ ai Δ f H V To illustrate the concept, let us consider
i the calculation of heat of reaction for the
(6.15) following reaction :
where a and b represent the coefficients of the
products and reactants in the balanced Fe 2 O3 ( s ) + 3H
equation. Let us apply the above equation for From the Table (6.2) of standard enthalpy of
decomposition of calcium carbonate. Here, formation (Δf H 0), we find :
coefficients ‘a’ and ‘b’ are 1 each.
Therefore, Δ f H V ( H2O,l ) = –285.83 kJ mol–1;
Δr H V = Δ f H V [ Δ f H V ( Fe 2 O 3 ,s = – 824.2 kJ mol–1;
Also Δ f H V (Fe
Δ f H V (H
=1( − 635.1 kJ
Then,
V
= 178.3 kJ mol–1 Δr H1 = 3(–285.83 kJ mol–1)
Thus, the decomposition of CaCO3 (s) is an – 1(– 824.2 kJ mol–1)
endothermic process and you have to heat it = (–857.5 + 824.2) kJ mol–1
for getting the desired products.
= –33.3 kJ mol–1
(d) Thermochemical equations Note that the coefficients used in these
A balanced chemical equation together with calculations are pure numbers, which are
the value of its ΔrH is called a thermochemical equal to the respective stoichiometric
equation. We specify the physical state coefficients. The unit for Δ r H 0 is
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
169
THERMODYNAMICS 169
kJ mol–1, which means per mole of reaction. Consider the enthalpy change for the
Once we balance the chemical equation in a reaction
particular way, as above, this defines the mole
of reaction. If we had balanced the equation C ( graphite,s )
differently, for example,
1 3 Although CO(g) is the major product, some
Fe2O3 ( s ) +
2 2 CO2 gas is always produced in this reaction.
Therefore, we cannot measure enthalpy change
then this amount of reaction would be one
for the above reaction directly. However, if we
mole of reaction and ΔrH 0 would be
can find some other reactions involving related
species, it is possible to calculate the enthalpy
V
Δr H 2 =
3
2
( − 28 change for the above reaction.
Let us consider the following reactions:
− ( − 824.2 kJ
1
2 C ( graphite,s )
–1 (i)
= (– 428.7 + 412.1) kJ mol
V
= –16.6 kJ mol–1 = ½ Δr H1 1
CO ( g ) + O2 (
It shows that enthalpy is an extensive quantity. 2 (ii)
3. When a chemical equation is reversed, the
value of ΔrH 0 is reversed in sign. For
example We can combine the above two reactions
in such a way so as to obtain the desired
N 2 (g) + 3H2 ( g reaction. To get one mole of CO(g) on the right,
we reverse equation (ii). In this, heat is
absorbed instead of being released, so we
2NH3 (g) → N 2 change sign of ΔrH 0 value
CO2 ( g ) → CO
(e) Hess’s Law of Constant Heat
Summation Δr H V = + 283. (iii)
We know that enthalpy is a state function,
therefore the change in enthalpy is Adding equation (i) and (iii), we get the
independent of the path between initial state desired equation,
(reactants) and final state (products). In other
words, enthalpy change for a reaction is the C ( graphite,s )
same whether it occurs in one step or in a
series of steps. This may be stated as follows
for which Δr H V = ( −39
in the form of Hess’s Law.
If a reaction takes place in several steps = – 110.5 kJ mol–1
then its standard reaction enthalpy is the In general, if enthalpy of an overall reaction
sum of the standard enthalpies of the A→B along one route is ΔrH and ΔrH1, ΔrH2,
intermediate reactions into which the
ΔrH3..... representing enthalpies of reactions
overall reaction may be divided at the same
leading to same product, B along another
temperature.
route,then we have
Let us understand the importance of this
law with the help of an example. ΔrH = ΔrH1 + ΔrH2 + ΔrH3 ... (6.16)
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
170
170 CHEMISTRY
13 1
C4 H10 (g) + H2 ( g ) + O2 (
2 2
Δf HV = −
Similarly, combustion of glucose gives out multiplying eqn. (iii) by 6 and eqn. (iv)
2802.0 kJ/mol of heat, for which the overall by 3 we get:
equation is : 6C ( graphite )
C6 H12 O6 (g) + 6 Δ
Δ
3
Our body also generates energy from food 3H2 ( g ) + O2
by the same overall process as combustion, 2
although the final products are produced after Δ
a series of complex bio-chemical reactions
involving enzymes. Summing up the above two equations :
6C ( graphite ) +
Problem 6.8
The combustion of one mole of benzene
takes place at 298 K and 1 atm. After
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
171
THERMODYNAMICS 171
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
172
172 CHEMISTRY
For example in CH4, ΔC–HH 0 is calculated as: products in gas phase reactions as:
ΔC−H H V = ¼ ( Δ Δr H V = ∑ bon
= 416 kJ mol–1 − ∑b
We find that mean C–H bond enthalpy in (6.17)**
methane is 416 kJ/mol. It has been found that This relationship is particularly more
mean C–H bond enthalpies differ slightly from useful when the required values of Δf H0 are
compound to compound, as in not available. The net enthalpy change of a
CH 3 CH 2 Cl,CH etc, but it does not differ reaction is the amount of energy required to
in a great deal*. Using Hess’s law, bond break all the bonds in the reactant molecules
enthalpies can be calculated. Bond enthalpy minus the amount of energy required to break
values of some single and multiple bonds are all the bonds in the product molecules.
given in Table 6.3. The reaction enthalpies are Remember that this relationship is
very important quantities as these arise from approximate and is valid when all substances
the changes that accompany the breaking of (reactants and products) in the reaction are in
old bonds and formation of the new bonds. We gaseous state.
can predict enthalpy of a reaction in gas phase,
(d) Enthalpy of Solution (symbol : ΔsolH )
0
if we know different bond enthalpies. The
standard enthalpy of reaction, ΔrH0 is related Enthalpy of solution of a substance is the
to bond enthalpies of the reactants and enthalpy change when one mole of it dissolves
–1
Table 6.3(a) Some Mean Single Bond Enthalpies in kJ mol
H C N O F Si P S Cl Br I
436 414 389 464 569 293 318 339 431 368 297 H
347 293 351 439 289 264 259 330 276 238 C
159 201 272 - 209 - 201 243 - N
138 184 368 351 - 205 - 201 O
159 540 490 327 255 197 - F
176 213 226 360 289 213 Si
213 230 331 272 213 P
213 251 213 - S
243 218 209 Cl
192 180 Br
151 I
–1
Table 6.3(b) Some Mean Multiple Bond Enthalpies in kJ mol
* Note that symbol used for bond dissociation enthalpy and mean bond enthalpy is the same.
** If we use enthalpy of bond formation, (Δf H bond
0
), which is the enthalpy change when one mole of a particular type of
bond is formed from gaseous atom, then Δ H = ∑ Δ H
V V
r f bonds
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
173
THERMODYNAMICS 173
1
3. Cl2 (g) → Cl( , the dissociation of
2
chlorine, the reaction enthalpy is half the
Δsol H V = Δlattice H
For most of the ionic compounds, Δsol H0 is
positive and the dissociation process is
endothermic. Therefore the solubility of most
salts in water increases with rise of
temperature. If the lattice enthalpy is very
high, the dissolution of the compound may not
take place at all. Why do many fluorides tend
to be less soluble than the corresponding
chlorides? Estimates of the magnitudes of
enthalpy changes may be made by using tables
of bond energies (enthalpies) and lattice
energies (enthalpies).
Lattice Enthalpy
The lattice enthalpy of an ionic compound is
the enthalpy change which occurs when one
mole of an ionic compound dissociates into its Fig. 6.9 Enthalpy diagram for lattice enthalpy
ions in gaseous state. of NaCl
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
174
174 CHEMISTRY
You have learnt about ionization enthalpy For one mole of NaCl(s),
and electron gain enthalpy in Unit 3. In lattice enthalpy = + 788 kJ mol–1
fact, these terms have been taken from and ΔhydH = – 784 kJ mol –1( from the
0
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
175
THERMODYNAMICS 175
1
H2(g) + O (g) → H2O(l) ;
2 2
Fig. 6.10 (b) Enthalpy diagram for endothermic
Δr H0 = –285.8 kJ mol–1 reactions
The decrease in enthalpy in passing from
reactants to products may be shown for any Therefore, it becomes obvious that while
exothermic reaction on an enthalpy diagram decrease in enthalpy may be a contributory
as shown in Fig. 6.10(a). factor for spontaneity, but it is not true for all
Thus, the postulate that driving force for a cases.
chemical reaction may be due to decrease in (b) Entropy and spontaneity
energy sounds ‘reasonable’ as the basis of Then, what drives the spontaneous process in
evidence so far ! a given direction ? Let us examine such a case
Now let us examine the following reactions: in which ΔH = 0 i.e., there is no change in
1 enthalpy, but still the process is spontaneous.
N (g) + O2(g) → NO2(g); Let us consider diffusion of two gases into
2 2
Δr H0 = +33.2 kJ mol–1 each other in a closed container which is
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
176
176 CHEMISTRY
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
177
THERMODYNAMICS 177
temperature. This suggests that the entropy (ii) At 0 K, the contituent particles are
change is inversely proportional to the static and entropy is minimum. If
temperature. ΔS is related with q and T for a temperature is raised to 115 K, these
reversible reaction as : begin to move and oscillate about
qrev their equilibrium positions in the
ΔS = (6.18) lattice and system becomes more
T
The total entropy change ( ΔStotal) for the disordered, therefore entropy
system and surroundings of a spontaneous increases.
process is given by (iii) Reactant, NaHCO3 is a solid and it
has low entropy. Among products
ΔStotal = ΔSsyste (6.19) there are one solid and two gases.
When a system is in equilibrium, the Therefore, the products represent a
entropy is maximum, and the change in condition of higher entropy.
entropy, ΔS = 0. (iv) Here one molecule gives two atoms
We can say that entropy for a spontaneous i.e., number of particles increases
process increases till it reaches maximum and leading to more disordered state.
at equilibrium the change in entropy is zero. Two moles of H atoms have higher
Since entropy is a state property, we can entropy than one mole of dihydrogen
calculate the change in entropy of a reversible molecule.
process by Problem 6.10
q sys ,rev For oxidation of iron,
ΔSsys =
T 4Fe ( s ) + 3O2 (
We find that both for reversible and entropy change is – 549.4 JK–1mol–1at
irreversible expansion for an ideal gas, under 298 K. Inspite of negative entropy change
isothermal conditions, ΔU = 0, but ΔStotal i.e., of this reaction, why is the reaction
ΔSsys + ΔSsurr is not zero for irreversible spontaneous?
process. Thus, ΔU does not discriminate (Δ r H 0 for this reaction is
between reversible and irreversible process, –1648 × 103 J mol–1)
whereas ΔS does. Solution
One decides the spontaneity of a reaction
Problem 6.9 by considering
Predict in which of the following, entropy
increases/decreases : ΔStotal ( ΔSsys + . For calculating
(i) A liquid crystallizes into a solid. ΔS surr, we have to consider the heat
(ii) Temperature of a crystalline solid is absorbed by the surroundings which is
raised from 0 K to 115 K. equal to – ΔrH 0. At temperature T, entropy
change of the surroundings is
( iii ) 2NaHCO
Δr H
ΔSsurr = −
T
(iv) H2 ( g ) → 2H ( g =−
( −1648 ×10
Solution 298
(i) After freezing, the molecules attain an = 5530 JK −1m
ordered state and therefore, entropy Thus, total entropy change for this
decreases. reaction
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
178
178 CHEMISTRY
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
179
THERMODYNAMICS 179
(a) The positive entropy change of the system at equilibrium the free energy of the system is
can be ‘small’ in which case T must be large. minimum. If it is not, the system would
(b) The positive entropy change of the system spontaneously change to configuration of
can be ’large’, in which case T may be small. lower free energy.
The former is one of the reasons why reactions So, the criterion for equilibrium
are often carried out at high temperature.
A + B ƒ C + D ; is
Table 6.4 summarises the effect of temperature
on spontaneity of reactions. ΔrG = 0
Gibbs energy for a reaction in which all
6.7 GIBBS ENERGY CHANGE AND reactants and products are in standard state,
EQUILIBRIUM 0
ΔrG is related to the equilibrium constant of
We have seen how a knowledge of the sign and the reaction as follows:
magnitude of the free energy change of a 0 = ΔrG0 + RT ln K
chemical reaction allows:
or ΔrG0 = – RT ln K
(i) Prediction of the spontaneity of the
chemical reaction. or ΔrG0 = – 2.303 RT log K (6.23)
(ii) Prediction of the useful work that could be We also know that
extracted from it. Δr G V = Δr H V − (6.24)
So far we have considered free energy For strongly endothermic reactions, the
changes in irreversible reactions. Let us now value of ΔrH 0 may be large and positive. In
examine the free energy changes in reversible such a case, value of K will be much smaller
reactions. than 1 and the reaction is unlikely to form
‘Reversible’ under strict thermodynamic much product. In case of exothermic reactions,
sense is a special way of carrying out a process ΔrH 0 is large and negative, and ΔrG0 is likely to
such that system is at all times in perfect be large and negative too. In such cases, K will
equilibrium with its surroundings. When be much larger than 1. We may expect strongly
applied to a chemical reaction, the term exothermic reactions to have a large K, and
‘reversible’ indicates that a given reaction can hence can go to near completion. ΔrG 0 also
proceed in either direction simultaneously, so depends upon ΔrS 0 , if the changes in the
that a dynamic equilibrium is set up. This entropy of reaction is also taken into account,
means that the reactions in both the directions the value of K or extent of chemical reaction
should proceed with a decrease in free energy, will also be affected, depending upon whether
which seems impossible. It is possible only if ΔrS 0 is positive or negative.
Δ rH 0 ΔrS 0 Δ rG 0 Description*
* The term low temperature and high temperature are relative. For a particular reaction, high temperature could even
mean room temperature.
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
180
180 CHEMISTRY
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
181
THERMODYNAMICS 181
SUMMARY
Δr H = ∑ (a Δ
f
i f H
K can be calculated from this equation, if we know ΔrG which can be found from
0
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
182
182 CHEMISTRY
EXERCISES
3
NH2CN(g) + O (g) → N2(g) + CO2(g) + H2O(l)
2 2
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
183
THERMODYNAMICS 183
3
O (g) → CO2(g) + 2H2O(l) ; ΔrH = –726 kJ mol–1
0
CH3OH (l) +
2 2
C(g) + O2(g) → CO2(g) ; ΔcH 0 = –393 kJ mol–1
1
H2(g) + O (g) → H2O(l) ; Δf H 0 = –286 kJ mol–1.
2 2
6.15 Calculate the enthalpy change for the process
CCl4(g) → C(g) + 4 Cl(g)
and calculate bond enthalpy of C – Cl in CCl4(g).
ΔvapH (CCl4) =
0
30.5 kJ mol–1.
ΔfH (CCl4) = –135.5 kJ mol–1.
0
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6
184
184 CHEMISTRY
6.20 The equilibrium constant for a reaction is 10. What will be the value
of ΔG0 ? R = 8.314 JK–1 mol–1, T = 300 K.
6.21 Comment on the thermodynamic stability of NO(g), given
1 1
N (g) + O (g) → NO(g) ; ΔrH0 = 90 kJ mol–1
2 2 2 2
1
NO(g) + O (g) → NO2(g) : ΔrH0= –74 kJ mol–1
2 2
6.22 Calculate the entropy change in surroundings when 1.00 mol of
H2O(l) is formed under standard conditions. Δf H0 = –286 kJ mol–1.
C:\Chemistry XI\Unit-6\Unit-6(3)-Lay-6.pmd 9.1.2006 (Final), 10.1.6, 13.1.6, 14.1.6, 17.1.6, 24.1.6, 17.2.6