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CHEMICAL THERMODYNAMICS
Can you recall ? putting certain mass on the piston. In this case,
1. How do you define energy? a gas under study is called the system.
2. What are the different forms of
Surrounding
energy?
Surrounding
Surrounding
water or burning of carbon forming carbon
dioxide, CO2, are accompanied by a change
in energy. In dry cell, the chemical energy is
converted into electrical energy. On the other Gas
(system)
hand, in electroplating of metals electrical
energy is converted into chemical energy. Fig. 4.1 : System and surroundings
Thus it may be realized that the energy can be A part of the universe under
transformed from one form into another. thermodynamic investigation is called
the system.All other parts of the universe
Do you know ? outside the system such as cylinder, room
and others, are surroundings. The universe
At the top of dam, water is
is made of system plus surroundings.
stored in a reservoir. It has certain
potential energy due to its height from ground 4.2.2 Types of system :
level and its kinetic energy is negligible as it
is not in motion. As the water starts to fall Observe and discuss...
down through an outlet its potential energy
Observe Fig. 4.2 and discuss
decreases and kinetic energy increases due
to the downward velocity. It means that with reference to transaction of
potential energy of falling water is converted energy and matter.
into kinetic energy.
Matter Insulator
Thermodynamics is concerned with the Energy Energy
energy changes in physical and chemical Matter
transformations. Thermodynamics, however
gives no information on the rates of physical or Energy Matter
chemical processes or underlying mechanisms Open system Closed system Isolated system
involved in these. (a) (b) (c)
63
surroundings. Such a system (coffee) which
exchanges both energy and matter with the
surroundings is called an open system.
ii. Closed system : In Fig. 4.2(b), a cup
containing hot coffee is covered with a saucer.
Coffee cools down by giving away heat to the
surroundings. The water vapour from coffee
now does not pass into surroundings. Such Fig. 4.3 : Change of state
a system that exchanges energy and not the
matter with the surroundings is called a closed Suppose the pressure of the system is
system. increased to 2 bar, (P2 ) volume changes to 0.5
dm3 (V2 ) and the temperature is maintained at
iii. Isolated system : As you see in Fig. 4.2(c),
300 K (T1 ). This is the final state of the system
a cup containing hot coffee covered with a
which is different from the initial state. A
saucer is insulated from the surroundings.
change in state functions of the system brings
Coffee does not cool down. Moreover,
forth a change of its state. This is shown in Fig.
there is no escape of water vapour into the
4.3.
surroundings. Such a system that does not
allow exchange of either energy or matter with The final state of the system in Fig. 4.3. is
the surroundings is an isolated system. described by pressure 2 bar (P2 ), volume 0.5
dm3(V2 ) and temperature 300 K(T1 ). A system
4.2.3 Properties of system
continues to be in such state as long as the state
i. Extensive property : functions are unchanged. How the pressure 2
A property which depends on the amount bar is attained whether by increasing from 1
of matter present in a system is called an bar to 2 bar or decreasing from 5 bar to 2 bar,
extensive property. would not matter.
Examples : Mass, volume, internal energy, The property which depends on the state
heat capacity, number of moles. of a system and independent of a path followed
to attain it, is called the state function.
ii. Intensive property :
The term process means a physical or
A property which is independent of the amount chemical change in a system on going from
of matter in a system is called intensive one state to another. This can be achieved by a
property. number of paths by some operation. A path here
Examples : Pressure, temperature, surface refers to a sequence of situations the system
tension, viscosity, melting point, boiling point, undergoes during the accomplishment of the
specific heat. change. In other words the process in general
may not necessarily determine the change in
4.2.4 State functions : As shown in Fig.
unique way. Only isothermal and adiabatic
4.1, certain amount of a gas is enclosed in a
reversible processes follow the unique path to
cylinder fitted with a movable piston. Suppose
bring about the change of state of the system.
the pressure of the gas is 1 bar (P1 ), volume is
1 dm3 (V1 ) and temperature is 300 K (T1 ) in 4.2.5 Path Functions : The properties which
the beginning. This initial state of the system depend on the path are called path functions.
is fully defined by specifying the values of For example, work (W) and heat (Q).
these properties. Such properties defining the
state of a system, are state functions.
64
4.2.6 Thermodynamic equilibrium : carried out in a closed container is isochoric.
Consider a gas enclosed in a cylinder fitted For isochoric process ∆V = 0.
with a movable piston shown in Fig. 4.1. iv. Adiabatic process : A process in which
The gas has temperature T1, pressure P1 and there is no exchange of heat between system
volume V1. These state functions continue to and surroundings is an adiabatic process.
be constant as long as piston is motionless, (Q = 0). In adiabatic process the system is
and no heat exchange takes place. This is an completely insulated from the surroundings.
equilibrium state. For an exothermic process the heat is released
Now move the piston in upward direction which rises temperature of the system. If the
so that the gas expands. It passes through states process is endothermic the temperature falls.
for which pressure, volume and temperature This results in either increase or decrease of
are not specified and vary continuously during internal energy.
the movement of the piston. The gas would v. Reversible process : Consider a gas enclosed
then be in nonequilibrium state. in a cylinder fitted with a movable piston.
Stop the movement of the piston. Suppose Let the external pressure be Pext on the outer
at this stage the pressure and volume of the gas surface of the piston be set equal to pressure P
are respectively P2 and V2 and the temperature of the gas. Neither expansion nor compression
is constant at T1. The state functions are of the gas occurs. A system is then said to be
constant since the piston is motionless. The in mechanical equilibrium with surroundings.
gas is then in another equilibrium state. Consider Pext is reduced by an infinitesimal
A system is said to be in thermodynamic amount. Now it the Pext is infinitesimally
equilibrium when its state functions do not smaller than P the piston moves out slowly
vary with time. Thermodynamics considered allowing gas to expand.
here is limited to equilibrium states. If Pext is slightly increased so that it
4.2.7 Process and its types : A transition becomes infinitesimally greater than P, the
from one equilibrium state to another is called piston moves inward with a compression of
a process. They are of different types. the gas.
i. Isothermal process : It is the process in For the system in mechanical equilibrium
which temperature of the system remains with its surroundings, infinitesimal change
constant throughout the transformation. may cause the process to occur in the reverse
In such process heat flows from the system direction. The process is then said to be
to surroundings and vice versa so as to keep the thermodynamically reversible. A process
temperature constant. For a given temperature conducted in such a way so that at every
the internal energy (U) of the system remains stage the driving force due to pressure (P) is
constant. Thus, ∆T = 0 and ∆U = 0. infinitesimally greater than the opposing force
due to external pressure (Pext) and which can
ii. Isobaric process :
In isobaric process be reversed by a slight change of the opposing
the pressure remains constant during the force is reversible process.
transformation. In the laboratory chemical
reactions are carried out in open containers at Features of reversible process
constant atmospheric pressure or ∆P = 0 i. The driving and opposing forces differ by an
iii. Isochoric process : It is a process during infinitesimal amount.
which volume of the system remains constant ii. The process can be reversed by an
during the transformation. A chemical reaction infinitesimal change in conditions.
65
iii. A reversible process proceeds infinitely surroundings. With no heat being transferred
slowly and takes place in infinite number of a loss of energy by the system is equal to work
steps. done by the system on the surroundings. This
iv. At the end of every step of the process, the is PV expansion.
system attains mechanical equilibrium with ii. Reaction between NH3 gas and HCl gas
the surroundings. Now, consider
4.3 Nature of heat and work NH3(g) + HCl(g) NH4Cl(s)
As the reaction progresses the gases are
4.3.1 Nature of work (W) : In mechanics the
consumed resulting in a decrease of volume.
work is defined as the energy by which body
The piston moves down. A decrease in the
is displaced through a distance d with an
height of the mass is shown in Fig. 4.5.
application of force. Thus,
W=f×d
In thermodynamics the type of work
involved is pressure-volume or PV work, that
is, work is done when the system (gas) expands
or contracts against the external opposing
force.
It may be realized that the product of
pressure and volume is equal to work. Pressure
is defined as force per unit area. If d is the Fig. 4.5 : Reaction between NH3(g) and HCl(g)
distance, area A = d2 and volume V = d3. Then
f f In the process the surroundings lose
PV = × V = 2 × d3 = f d = W energy to the system and perform work on the
A d
Now let us explore the PV work with system. If no heat transfer occurs work done
two chemical reactions in a cylinder equipped by the surroundings is equal to gain in energy
with frictionless movable piston attached with by the system. This is PV work.
a certain mass on its outer surface.
Thus the work refers to a way by which
i. Decomposition of H2O2 a system exchanges energy with surroundings.
Consider 2 H2O2(l) 2 H2O(l) + O2(g)
4.3.2 Nature of heat (Q) : Like heat is a form of
energy by which the system exchanges energy
with its surroundings. When the system and its
surroundings are at different temperatures heat
either flows in or let out of the system.
O2(g) 4.3.3 Sign conventions of W and Q : The
energy changes for the system are considered
H2O2 hereafter.
The energy entering the system from the
surroundings has positive value. While the
Fig. 4.4 : Decomposition of H2O2
energy leaving the system and flowing into the
The gas produced in above reaction surroundings is negative. This is shown in Fig.
pushes the piston upwards so that the mass in 4.6.
the surroundings is raised as shown in Fig. 4.4.
+Q : Heat is absorbed by the system from the
In lifting the mass the system loses energy to
surroundings.
the surroundings or it performs work on the
66
W = f × d (4.2)
Substitution from Eq. (4.1) gives
W = - Pext × A × d (4.3)
The product of area of the piston and
Fig. 4.6 : Sign conventions
distance it moves is the volume change (∆V)
in the system.
-Q : Heat is released by the system to the
surroundings. ∆V = A × d (4.4)
+W : Work is done on the system by the Combining equations (4.3) and (4.4) we write
surroundings. W = - Pex ∆V (4.5)
-W : Work is done by the system on the
W = - Pex (V2 - V1)
surroundings.
where V2 is final volume of the gas.
Note W and Q are path functions.
When the gas expands, work is done by the
4.4 Expression for pressure-volume (PV)
work : Consider a certain amount of gas at system on the surroundings. Since V2 > V1, W
constant pressure P is enclosed in a cylinder is negative. When the gas is compressed, work
fitted with frictionless, rigid movable piston of is done on the system by surroundings. In this
area A. This is shown in Fig. 4.7. case V1< V2, and -Pext ∆V or W is positive.
Eq. (4.5) shows the external pressure
determines the work during expansion (or
compression) of the gas. A volume change
does no work unless the system is linked to the
surroundings by external pressure.
Remember...
Remember during expansion
of a gas, work is done by the
Fig. 4.7 : Pressure-volume work system on the surroundings and during
compression work is done on the system by
Let volume of the gas be V1 at temperature T. the surroundings.
On expansion the force exerted by a
gas is equal to area of the piston multiplied 4.4.1 Free expansion : A free expansion
by pressure with which the gas pushes against means expansion against zero opposing force.
piston. This pressure is equal in magnitude and Such expansion occurs in vacuum. The work
opposite in sign to the external atmospheric done by a system during such expansion is
pressure that opposes the movement and has given by Eq. (4.5), W = - Pext ∆V. When the
its value -Pext. Thus, gas expands in vacuum, there is no opposing
force that is Pext and hence, W = 0. In other
f = -Pext × A (4.1)
words no work is done when the gas expands
where Pext is the external atmospheric pressure. freely in vacuum.
If the piston moves out a distance d,
then the amount of work done is equal to the
force multiplied by distance.
67
4.4.2 Units of energy and work Problem 4.3 : 200 mL ethylene gas and 150
1 J = 1 kg m s = 1 Pa m
2 -2 3
mL of HCl gas were allowed to react at 1
1 Pa = 1 kg m-1 s-2 bar pressure according to the reaction
68
The work (W) would be maximum When the volume of a gas increases by
when ∆P is smallest. This means the opposing an infinitesimal amount dV in a single step, the
force (Pex) must be infinitesimally smaller small quantity of work done
than the driving force (P) for the work to be dW = -Pext dV (4.6)
maximum. This is required for the process to
be reversible. The maximum work is obtained As the expansion is reversible, P is greater by
from the change which is thermodynamically a very small quantity dp than pex. Thus,
reversible. P -Pext = dP or Pext = P - dP (4.7)
4.5.1 Expression for the maximum work : Combining equations (4.6) and (4.7),
Consider n moles of an ideal gas enclosed dW = - (P - dP)dV = - PdV + dP dV
in a cylinder fitted with frictionless movable
Neglecting the product dpdV which is very
rigid piston. It expands isothermally and
small, we get
reversibly from the initial volume V1 to final
volume V2 at temperature T. The expansion dW = - PdV (4.8)
takes place in a number of steps illustrated in The total amount of work done during
Fig. 4.8. entire expansion from volume V1 to V2 would
be the sum of infinitesimal contributions of
all the steps. The total work is obtained by
Step 1 Step 2 Step 3 Continued integration of Eq. (4.8) between the limits of
initial and final states. This is the maximum
work, the expansion being reversible. Thus,
dv
dv dv final
v2
V1
Gas Gas Gas Gas
∫ dW
initial
=- ∫ PdV
v1
v2
69
Replacing V2/V1 in Eq. (4.10) by P1/P2, We
have Problem 4.6 : 300 mmol of an ideal gas
P occupies 13.7 dm3 at 300 K. Calculate the
Wmax = -2.303 nRT log 1 (4.11) work done when the gas is expanded until
P2
its volume has increased by 2.3 dm3 (a)
Problem 4.4 : 2 moles of an ideal gas are isothermally against a constant external
expanded isothermally and reversibly from pressure of 0.3 bar (b) isothermally and
20 L to 30 L at 300 K. Calculate the work reversibly (c) into vacuum.
done (R= 8.314 J K-1 mol-1) Solution :
V
Solution : Wmax = -2.303 nRT log10 2 a. W = -Pex ∆V
V1
n = 2 mol, T = 300 K, V1 = 20 L, V2 = 30 L, Pext = 0.3 bar, ∆V = 2.3 dm3
R = 8.314 J/K mol W = -0.3 bar × 2.3 dm3
Substitution of these quantities into the = -0.69 dm3 bar
equation gives 100 J
= -0.69 dm3 bar ×
dm3 bar
Wmax = -2.303 × 2 mol × 8.314 J/K mol × = - 69 J
300K × log10 30 L V
20 L b. Wmax = - 2.303 nRT log10 2
= -2.303 × 2 × 8.314 J×300 × log10 1.5 V1
= -2.303 × 2 × 8.314 J×300 × 0.1761 n = 300 mmol = 300 × 10 mol = 0.3 mol,
-3
T = 300 K
= -2023 J = -2.023 kJ
Wmax = - 2.303 × 0.3 mol × 8.314 J K-1mol-1
Problem 4.5 : 22 g of CO2 are compressed
16
isothermally and reversibly at 298 K from × 300K × log10
13.7
initial pressure of 100 kPa when the work
= -2.303 ×0.3 ×8.314 J ×300 ×0.0674
obtained is 1.2 kJ. Find the final pressure.
= - 116.1 J
Solution :
P1 c. W = - Pex ∆V
W = -2.303 nRT log10 When gas is expanded to vaccum, Pext = 0
P2
22 g and W = 0
n= =0.5 mol, T = 298 K,
44 g mol-1
P1= 100 kPa, W = 1.2 kJ = 1200 J 4.6 Internal energy (U) : Every substance is
associated with a definite amount of energy.
Hence, 1200 J = -2.303 × 0.5 mol ×8.314 J This energy stored in a substance is internal
100 kPa energy denoted by U.
K-1 mol-1 × 298K × log10
P2 The internal energy of a system is made up
of kinetic and potential energies of individual
or log10 100 kPa =
P2 particles of the system.
-1200 ∆U = U2 - U1
2.303 ×0.5 ×8.314 ×298
where U1 and U2 are internal energies of initial
= -0.4206
and final states, respectively. U is a state
100 kPa function and extensive property.
= antilog (-0.4206) = 0.3797
P2
100 kPa
Therefore, P2 = 0.3797 = 263.4 kPa
70
4.7.1 Formulation of first law of
Try this...
thermodynamics : A system exchange energy
25 kJ of work is done on the with its surroundings either by transfer of
system and it releases 10 kJ of heat or by doing work. An energy supplied
heat. What is ∆U? to the system increases its internal energy.
On the other hand, removal of heat or work
A transfer of energy (as heat or work) from the system decreases its internal energy.
from the system would change its internal Suppose (Q) is heat supplied to the
energy. To know ∆U the energy supplied to or system and W work done on the system by
removed from the system need to be monitored. the surroundings. The internal energy of the
i. The energy transferred to the system by system would increase.
heating it or performing work on it is added Increase in internal energy of the system
to the system. is equal to sum of the quantity of heat supplied
ii. The energy transferred from the system to the system and amount of work done on the
by cooling or by performing work on the system or
surroundings is removed from the system. ∆U = Q + W (4.12)
The following examples illustrate how to where ∆U is an increase in internal energy
determine ∆U. of the system. Eq. (4.12) is the first law of
i. 30 kJ of heat supplied to the system. It thermodynamics. For infinitesimal changes.
would be added to internal energy of the dU = dQ +dW (4.13)
system and ∆U = +30 kJ. 4.7.2 First law of thermodynamics for
ii. If 20 kJ of work is done on the system, it various processes
is added to internal energy of the system. i. Isothermal process : Temperature is constant
Consequently, ∆U = + 20 kJ. in such process, internal energy is constant.
iii. Suppose a system releases 10 kJ of heat and Hence, ∆U = 0
performs 15 kJ of work on the surroundings. For isothermal process
These quantities are removed from internal 0 = Q +W or W = -Q (4.14)
energy of the system and ∆U = - 25 kJ
The above equation implies that heat
4.7 First law of thermodynamics : First law absorbed by the system is entirely used for
of thermodynamics is simply the conservation doing work on the surroundings. When work
of energy. According to this law the total is done on the system by the surroundings it
energy of a system and surroundings remains results in release of heat.
constant when the system changes from an
ii. Adiabatic process : In adiabatic process,
initial state to final state. The law is stated in
there is no exchange of heat between system
different ways as follows.
and its surroundings that is, Q = 0. then
i. Energy of the universe remains constant -∆U = -W (4.15)
ii. The total internal energy of an isolated Thus an increase in internal energy of
system is constant the system is the work done on it. If the work
iii. Energy is neither created nor destroyed is done by the system on the surroundings at
and can only be converted from one form to the expense of its internal energy, the internal
another. energy accompanying the adiabatic process
All above statements are equivalent. would decrease.
71
iii. Isochoric process : Substitution of From Eq. (4.19), we write
W = -Pext ∆V into Eq. (4.12) H1 = U1 + P1V1 and H2 = U2 + P2V2
∆U = Q - Pext ∆V (4.16) With these
As the reaction is carried out in a closed ∆H = U2 + P2V2 - U1 + P1V1
container, volume of the system is constant or = (U2 - U1) + (P2V2 - P1V1)
∆V = 0 and
= ∆U + ∆(PV) (4.21)
∆U = Qv (4.17)
For constant pressure, P1 = P2 = P and
Equation (4.17) shows a change in
internal energy of the system is due to heat ∆H = ∆U + P∆V (4.22)
transfer at constant volume. The subscript ‘V’ If the pressure inside and outside is the same or
indicates that heat is transferred at the constant Pext = P, Eq. (4.18) gives
volume. Further U being a state function, Qv is
Qp = ∆U + P ∆V (4.23)
also a state function.
From equations (4.22) and (4.23)
iv. Isobaric process : Usually chemical
reactions are carried out in the open containers ∆H = Qp (4.24)
under constant atmospheric pressure. In such Thus change in enthalpy of a system is
reactions, ∆V ≠ 0 equal to heat transferred from it at the constant
Replacing Q by Qp and ∆U by Qp - Pext ∆V in pressure. H and Qp are state functions.
equation (4.16) gives 4.8.1 Relationship between ∆H and ∆U for
Qp = ∆U + Pext ∆V (4.18) chemical reactions : At constant pressure, ∆H
and ∆U are related as
The reactions carried out in open
containers under constant atmospheric ∆H = ∆U + P∆V
pressure are common in chemistry, a special i. For reactions involving solids and liquids, ∆V
symbol ∆H, the enthalpy change, is given to usually is very small (solids or liquids do not
indicate heat changes occurring at constant show volume change with change of pressure)
pressure. and ∆H = ∆U
Remember... ii. For reactions involving gases, ∆V cannot be
q is not a state function. neglected and
Whereas Qv and Qp are state ∆H = ∆U + P∆V
functions.
= ∆H + P(V2 - V1)
4.8 Enthalpy (H) : Enthalpy of a system is ∆H = ∆U + PV2 - PV1 (4.25)
sum of internal energy of a system and the
where V1 is the volume of gas phase reactants
energy equivalent to PV work.
and V2 that of the gaseous products.
H = U + PV (4.19)
We assume reactant and product behave
Change in enthalpy, ∆H, is also state ideally. Applying ideal gas equation PV = nRT.
function given by When n1 moles of gaseous reactants produce
∆H = H2 - H1 (4.20) n2 moles of gaseous products. The ideal gas
equation give,
where H1 and H2 are the enthalpies of initial
and final states, respectively. PV1 = n1RT and PV2 = n2RT (4.26)
72
Substitution of Eq. (4.26) into Eq. (4.25) yields Problem 4.9 : Calculate the work done in
∆H = ∆U + n2RT - n1RT oxidation of 4 moles of SO2 at 250C if
= ∆U + (n2- n1) RT 2 SO2(g) + O2(g) 2 SO3(g)
= ∆U + ∆ng RT (4.27) R = 8.314 J K-1mol-1
where ∆ng is difference between the number of State whether work is done on the system or
moles of products and those of reactants. by the system.
Solution :
Problem 4.7 : ∆H for the reaction,
For oxidation of 4 moles of SO2, the reaction
2C(s) + 3H2(g) C2H6(g) is -84.4 is
kJ at 25 C. Calculate ∆U for the reaction
0
4 SO2(g) + 2 O2(g) 4 SO3(g)
at 25 0C. (R = 8.314 J K-1 mol-1)
W = -∆ng RT
Solution :
∆ng = 4 - 6 = - 2 mol, T = 298 K
∆H = ∆U + ∆ng RT
Hence,
∆ng = (moles of product gases) - (moles of
reactant gases) W = -2 mol × -8.314 J K-1 mol-1 × 298 K
∆H = -84.4 kJ, R = 8.314 J K-1 mol-1 Work is done on the system (since W > 0).
75
On the other hand, if l (liquid), g (gas) and aq (aqueous). ∆rH0
∑ Hproducts < ∑ Hreactants, ∆rH is negative value refers to physical states of substances
those appear in the equation.
which means that heat is released and the
iv. The given value of ∆rH0 assumes that the
reaction is exothermic.
reaction occurs in a given direction. ∆rH0 for
For example, the reverse reaction equals in magnitude and
N2(g) + O2(g) 2 NO2(g), opposite in the sign to that of the forward
reaction. A exothermic reaction on reversal
∆rH = 66.4 kJ (endothermic) becomes endothermic and vice versa.
2 KClO3(s) 2 KCl(s) + 3O2(g), v. When the coefficients indicating the
∆rH = -78 kJ (exothermic) number of moles of all substances in
thermochemical equation are multiplied or
4.10.3 Standard enthalpy of reaction(∆rH0) divided by a certain numerical factor, the
To compare enthalpy changes of different corresponding ∆rH0 need to be multiplied or
reactions they have to be reported under similar divided by the same.
set of conditions. Example of thermochemical equation
Thermodynamic standard state : The CH4(g) + 2 O2(g) CO2(g) + 2H2O(l),
standard state of a substance is the form ∆rH0 = -890 kJ
in which the substance is most stable at a
The equation signifies that when 1 mole
pressure of 1 bar and at temperature 298 K.
of gaseous CH4 and 2 moles of O2 in their
If the reaction involves species in solution its
standard states produce 1 mole of CO2 gas and
standard state refers to 1 M concentration.
2 moles of liquid water also in their standard
Standard states of certain elements and states the enthalpy change would be -890 kJ.
compounds are H2(g), Hg(g), Na(s) or
C(graphite), C2H5OH(l), CaCO3(s), CO2(g) Try this...
C2H5OH(l), H2O(l), CaCO3(s), CO2(g) refer to Given the thermochemical equation,
1 bar and 25 0C. C2H2(g)+ 5/2 O2(g)
The standard enthalpy (∆rH ) of 0 2CO2(g)+ H2O(l),
reaction is the enthalpy change accompanying ∆rH0 = -1300 kJ
the reaction when the reactants and products Write thermochemical equations when
involved are in their standard states. i. Coefficients of substances are multiplied
4.10.4 Thermochemical equation : It is by 2.
the balanced chemical equation in which ii. equation is reversed.
the enthalpy change, physical states and the 4.10.5 Standard enthalpy of formation
number of moles of reactants and products, (∆fH0)
have been specified. Here follow the guidelines
for writing thermochemical equations : Consider
1
i. Consider the balanced equation for H2(g) + 2 O2(g) H2O(l), ∆rH0 = -286 kJ
reactants and products. For the reaction where one mole of
ii. The value and appropriate sign of enthalpy liquid water in standard state is formed from
change is given on the right hand side. This H2 and O2 gases in their standard states, the
value is ∆rH0. enthalpy changes for the reaction would be the
iii. The physical states of reactants and standard enthalpy of formation of water. ∆fH
products are specified by letter, s (solid), of water is -286 kJmol-1.
76
The standard enthalpy of formation = [c ∆fH0(C) + d ∆fH0(D)] -
of a compound is the enthalpy change that [a ∆fH0(A) + b ∆fH0(B)]
accompanies a reaction in which one mole
of pure compound in its standard state is = ∑ ∆fH0 (products) - ∑ ∆fH0 (reactants)
formed from its elements in their standard (4.30)
states.
Problem 4.10
The formation of one mole of CH4 in its
Calculate standard enthalpy of reaction,
standard state from the elements carbon and
hydrogen in their standard states is represented 2C2H6(g) +7O2(g) 4 CO2(g) + 6 H2O(l)
by Given that
C(graphite)+ 2H2(g) CH4(g), ∆rH = -74.8 kJ
0
∆fH0 (CO2)= -393.5 kJ mol-1,
or ∆fH0 (CH4) = -74.8 kJ mol-1 ∆fH0 (H2O)= -285.8 kJ mol-1 and
∆fH0(C2H6) = -84.9 kJ mol-1
Do you know ?
Solution -
The reaction to form a
substance from its constituent ∆rH0 = ∑ ∆fH0(products) - ∑ ∆fH0(reactants)
elements is hypothetical. It is not possible = [4 ∆fH0(CO2) + 6 ∆fH0(H2O)]
to combine C and H2 in the laboratory to
prepare CH4. The enthalpy of reaction - [2 ∆fH0(C2H6) + 7 ∆fH0(O2)]
for the formation of CH4 can be obtained = [4 mol × (-393.5 kJ mol-1) + 6 mol ×
indirectly by knowing the standard enthalpy (-285.8 kJ mol-1)]
change for system. The value -74.8 kJ mol-1
- [2 mol × (-84.9 kJ mol-1) + 0]
corresponds to the hypothetical reaction.
= -1574 kJ - 1714.8 kJ + 169.8 kJ
4.10.6 Standard enthalpy of reaction from
= -3119 kJ
standard enthalpies of formation
The standard enthalpies of formation 4.10.7 Standard enthalpy of combustion
of compounds are used to determine standard (∆cH0)
enthalpies of reactions. Consider the reaction
5
Calculations of ∆rH0 from ∆fH0 of C2H2(g) + O2(g) 2 CO2(g) + H2O(l),
2
compounds are based on the following. ∆rH0 = -1300 kJ
i. Standard enthalpies of formation of an In the above reaction, the standard enthalpy
element is zero. change of the oxidation reaction, -1300 kJ
is the standard enthalpy of combustion of
∆fH0(H2) = ∆fH0(Cl2) = ∆fH0(C) = 0
C2H2(g).
ii. Standard enthalpy of formation of a
The standard enthalpy of combustion of a
compound is equal to its standard enthalpy
substnce is the standard enthalpy change
∆fH0(compound) = H0(compound) accompanying a reaction in which one mole
Consider the reaction of the substance in its standard state is
completely oxidised.
aA + bB cC + dD
Standard enthalpy of the reaction is given by
∆fH0 = (cH0C+ dH0D) - (aH0A + bH0B)
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Try this... Remember...
For diatomic molecules the bond
Write thermochemical equation enthalpy is the same as enthalpy
for complete oxidation of one mole of atomization.
of H2(g). Standard enthalpy change of the
reaction is -286 kJ. HCl molecule dissociates as
Is the value -286 kJ, enthalpy of HCl(g) H(g) + Cl(g), ∆rH0 = 431.9 kJ
formation or enthalpy of combustion or
both? Explain. ∆H0 (H-Cl bond) = 431.9 kJ mol-1
Average bond enthalpy in polyatomic
Problem 4.11: Estimate the standard molecules : Each covalent bond in polyatomic
enthalpy of combustion of CH4(g) if molecules is associated with its own specific
∆fH0(CH4) = -74.8 kJ mol-1, ∆fH0(CO2) = bond enthalpy. The thermochemical equation
-393.5 kJ mol-1 and ∆fH0(H2O) = -285.8 kJ for dissociation of H2O molecules is
mol-1
H2O(g) 2 H(g) + O(g), ∆rH0 = 927 kJ
Solution : The equation for the combustion
The above equation implies that the
of CH4 is
enthalpy change for breaking of two O-H
CH4(g) + 2O2(g) CO2(g) + 2H2O(l),
∆rH0 = ? bonds in one mole of gaseous H2O molecules
is 927 kJ. Two O-H bonds in H2O are identical
∆rH0 = [∆fH0 (CO2) + 2 ∆fH0(H2O)] the energies needed to break individual O-H
-[∆fH0(CH4) + 2 ∆fH0(O2)] bonds are different.
= [1 × (-393.5) + 2 × (-285.8)] The bonds in H2O are broken in
- [1 × (-74.8) + 2 × 0] successive steps as shown
∆cH0(CH4) = -890.3 kJ i. H2O(g) OH(g) + H(g) ∆rH0 = 499 kJ
ii. OH(g) O(g) + H(g) ∆rH0 = 428 kJ
4.10.8 Bond enthalpy
Consider the reaction H2O(g) 2 H(g) + O(g) ∆rH0 = 927 kJ
H2(g) H(g) + H(g), ∆rH0 = 436.4 kJ The total enthalpy change, 927 kJ, not
It shows that H-H bond in one mole twice as large of the O-H bond enthalpy. What
of H2(g) is decomposed producing gaseous H is the enthalpy of O-H bond in H2O molecule?
atoms. The enthalpy change of the reaction, For polyatomic molecules the average
436.4 kJ is bond enthalpy of the H-H bond. bond enthalpy of a particular bond would be
The enthalpy change required to break considered. Thus, the average bond enthalpy
particular covalent bond in one mole of of the O-H bond = 927 2 = 463.5 kJ or ∆H0
gaseous molecule to produce gaseous atoms (O-H) = 463.5 kJ mol-1
and/or radicals, is called bond enthalpy.
Try this...
Write equation for bond
enthalpy of Cl-Cl bond in Cl2
molecule ∆rH0 for dissociation of Cl2
molecule is 242.7 kJ
78
Do you know ? Examples 4.12 : Calculate the standard
In CH4 molecule there are four enthalpy of :
identical C-H bonds. The bond N2H4(g) + H2(g) 2 NH3(g)
enthalpy of all the 4 C-H bonds are different. if ∆H0(N-H) = 389 kJ mol-1, ∆H0(H-H) = 435
The breaking of C-H bonds in CH4 occurs kJ mol-1, ∆H0 (N-N) = 159 kJ mol-1
in four steps as follows:
Solution :
CH4(g) CH3(g) + H(g), ∆rH0 = 427 kJ
H H H
CH3(g) CH2(g) + H(g), ∆rH0 = 439 kJ N N (g) + H-H(g) 2N H
CH2(g) CH(g) + H(g), ∆rH0 = 452 kJ H H H
CH(g) C(g) + H(g), ∆rH0 = 347 kJ ∆rH0 = ∑ ∆H0 (reactant) -
CH4(g) C(g) + 4 H(g), ∆rH0 = 1665 kJ ∑ ∆H0 (product)
Average C-H bond enthalpy = [4∆H0(N-H) + ∆H0(N-N)
= 1665 kJ/4 = 416 kJ + ∆H (H-H)] - [6 ∆H0(N-H)]
0
79
4.10.9 Hess’s law of constant heat summation
Solution :
The law states that, “Overall the
Reverse Eq.(i) and then add to Eq. (ii)
enthalpy change for a reaction is equal to
sum of enthalpy changes of individual steps 2Fe(s) + Al2O3(s) 2 Al(s) + Fe2O3(s),
in the reaction”. ∆rH0 = +847.6 kJ
The enthalpy change for a chemical 2 Al(s) + 3/2 O2(g) Al2O3(s),
reaction is the same regardless of the path by ∆rH0 = -1670 kJ
which the reaction occurs. Hess’s law is a direct
consequence of the fact that enthalpy is state 2Fe(s) + 3/2 O2(g) Fe2O3(s),
function. The enthalpy change of a reaction ∆rH0 = -822.4 kJ
depends only on the initial and final states and
not on the path by which the reaction occurs.
To determine the overall equation Example 4.15 : Calculate the standard
of reaction, reactants and products in the enthalpy of the reaction,
individual steps are added or subtracted like SiO2(s) + 3C(graphite) SiC(s) + 2 CO(g)
algebraic entities. from the following reactions,
Consider the synthesis of NH3 i. Si(s) + O2(g) SiO2(s),
i. 2H2(g) + N2(g) N2H4(g), ∆rH0 = -911 kJ
∆rH10 = + 95.4 kJ ii. 2 C(graphite) + O2(g) 2CO(g),
ii. N2H4(g) + H2(g) 2 NH3(g), ∆rH0 = -221 kJ
∆rH20 = -187.6 kJ iii. Si(s) + C(graphite) SiC(s),
∆rH0 = -65.3kJ
3 H2(g) + N2(g) 2 NH3(g),
Solution : Reverse the Eq. (i)
∆rH0 = -92.2 kJ
iv. SiO2(s) Si(s) + O2(g),
The sum of the enthalpy changes for
steps (i) and (ii) is equal to enthalpy change ∆rH0 = -911 kJ
for the overall reaction. Add equations (ii), (iii) and (iv)
Application of Hess’s law ii. 2 C(graphite) + O2(g) 2 CO(g),
The Hess's law has been useful to calculate the ∆rH = -221 kJ 0
enthalpy changes for the reactions with their iii. Si(s) + C(graphite) SiC(s),
enthalpies being not known experimentally. ∆rH = -65.3 kJ
0
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4.11 Spontaneous (irreversible) process : processes tend to occur in a direction
Spontaneous processes have a natural that leads to equilibrium.
tendency to occur and do not require any 4.11.1 Energy and spontaneity :
external influence for their occurrence. The spontaneous reaction takes place
in a direction in which energy of the system
Do you know ?
is lowered. It is accompanied by release of
i. The aqueous NaOH and energy. The reaction between NaOH and
HCl solutions mixed together. HCl is exothermic (∆rH° = -57 kJ) and is
NaOH immediately combines with spontaneous.
HCl to form NaCl and water.
On the other hand :
NaOH(aq)+HCl(aq) NaCl(aq)+ H2O(l),
∆rH0 = -57 kJ i. Ice melts spontanoeusly above 0 °C by
absorbing heat from the surroundings. It
No external force or energy is required
is endothermic.
for the reaction to occur. This is
spontaneous. The process stops when ii. Likewise, NaCl dissolves spontaneously in
HCl or NaOH is consumed. water with the absorbtion of heat from the
surroundings.
NaCl is dissolved in water, it does not
react with water to produce NaOH NaCl(s) + aq Na⊕(aq) + Cl (aq)
and HCl. ∆H = +3.9 kJ mol-1
0
82
From above examples, it is clear that From above,
the entropy of the system increases in the i. ∆Stotal > 0, the process is spontaneous
spontaneous processes. Consider the reaction.
ii. ∆Stotal < 0, the process is nonspontaneous
2H2(g) + O2(g) 2H2O(l),
iii. ∆Stotal = 0, the process is at equilibrium
∆S = -327 J K-1.
4.11.5 Gibbs energy
The entropy of the system decreases.
Note the reaction is spontaneous. As pointed out in the preceding section, it
is necessary to determine, ∆Ssys and ∆Ssurr, for
4.11.4 Second law of thermodynamics : predicting the spontaneity of a reaction. We
The second law of thermodynamics are more interested in the system (reaction
states that total entropy of a system and mixture) . It. is, therefore convenient to
its surroundings increases in a spontaneous consider the criterion of spontaneity in terms
process. For the process to be spontaneous of the thermodynamic properties of a system.
∆Stotal = ∆Ssys + ∆Ssurr > 0 (4.33) This problem was solved by American
theoretician J. W. Gibbs. He introduced a new
Consider thermodynamic property called Gibbs energy
2H2(g) + O2(g) 2H2O(l) usually denoted by G.
∆S = -327 J K-1, and ∆H = -572 kJ (both at The Gibbs energy is defined as
298 K) G = H - TS (4.34)
To find ∆Stotal, we need to know ∆Ssurr. where H is enthalpy and S entropy of the
∆H for the reaction is -572 kJ. When 2 moles system. Since H, T and S are state functions,
of H2 and 1 mole of O2 gas combine to form G is state function. A change in Gibbs energy
2 moles of liquid water, 527 kJ of heat is depends on initial and final states of the
released which is received by surroundings at system and not on a path connecting the two
constant pressure (and 298 K). The entropy states.
change of surroundings is
The change in Gibbs energy at constant
Q 572 × 103 J
∆Ssurr = rev = = 1919 J K-1 temperature and constant pressure is given by
T 298 K
∆Stotal = ∆Ssys + ∆Ssurr ∆G = ∆H - T ∆S (4.35)
= -327 J K-1 + 1919 J K-1 4.11.6 Gibbs energy and spontaneity
= + 1592 J K-1 The total entropy change that
accompanies a process is given by
∆Stotal > 0.
∆Stotal = ∆Ssys + ∆Ssurr
The reaction is thus spontaneous. It
follows that to decide spontaneity of reactions, = ∆S + ∆Ssurr (4.36)
we need to consider the entropy of system and The subscript sys that refers to the system
its surroundings. is dropped hereafter.
The total entropy increases during a Relation between ∆G and ∆Stotal
spontaneous process that finally reaches
equilibrium. The equilibrium corresponds to According to second law of
maximum total entropy. The total entropy thermodynamics for a process to be
change, ∆Stotal must be zero for a process at spontaneous, ∆ Stotal > 0
equilibrium.
83
If ∆H is the enthalpy change 3. For ∆H negative and ∆S is positive it
accompanying a reaction (system) the follows that ∆G is negative regardless of
enthalpy change of the surroundings is -∆H. temperature.
With 4. For ∆H positive and ∆S is negative then
∆Ssurr = - ∆H (4.37) ∆G is positive regardless of temperature.
T
Such reactions are nonspontaneous at all
Substituting above into Eq. (4.36), temperatures.
84
When the reaction reaches equilibrium, ∆G0 = 0 Problem 4.17
and Qc and Qp become Kc and Kp, respectively.
Thus, For a certain reaction ∆H0 is -224 kJ
and ∆S is -153 J K-1. At what temperature
0
85
Problem 4.19 : Calculate ∆Stotal and state Problem 4.20 : Calculate ∆G for the
whether the reaction is spontaneous or reaction at 25 0C
nonspontaneous at 25 0C. CO(g) + 2 H2(g) CH3OH(g), ∆G0
HgS(s) + O2(g) Hg(l) + SO2(g), = -24.8 kJ mol The partial pressures of
-1
Exercises
86
iv. The enthalpy of formation for all x. Bond enthalpies of H-H, Cl-Cl and
elements in their standard states is H-Cl bonds are 434 kJ mol-1, 242 kJ
a. unity mol-1 and 431 kJ mol-1, respectively.
Enthalpy of formation of HCl is
b. zero
a. 245 kJ mol-1 b. -93 kJmol-1
c. less than zero
c. -245 kJ mol-1 d. 93 kJ mol-1
d. different elements
2. Answer the following in one or two
v. Which of the following reactions is sentences.
exothermic?
i. Comment on the statement: no work
a. H2(g) 2H(g) is involved in an expansion of gas in
b. C(s) C(g) vacuum.
c. 2 Cl(g) Cl2(g) ii. State the first law of thermodynamics.
d. H2O(s) H2O(l) iii. What is enthalpy of fusion?
vi. 6.24 g of ethanol are vaporized by iv. What is standard state of a substance?
supplying 5.89 kJ of heat. Enthalpy v. State whether ∆S is positive, negative
of vaporization of ethanol will be or zero for the reaction 2H(g)
a. 43.4 kJ mol-1 H2(g). Explain.
b. 60.2 kJ mol-1 vi. State second law of thermodynamics
in terms of entropy.
c. 38.9 kJ mol-1
vii. If the enthalpy change of a reaction
d. 20.4 kJ mol-1
is ∆H how will you calculate entropy
vii. If the standard enthalpy of formation of surroundings?
of methanol is -238.9 kJ mol-1 then
viii. Comment on spontaneity of reactions
entropy change of the surroundings
for which ∆H is positive and ∆S is
will be
negative.
a. -801.7 J K-1 b. 801.7 J K-1
3. Answer in brief.
c. 0.8017 J K-1 d. -0.8017 J K-1
i. Obtain the relationship between ∆G0
viii. Which of the following are not state of a reaction and the equilibrium
functions? constant.
1. Q + W 2. Q 3. W 4. H-TS ii. What is entropy? Give its units.
a. 1,2 and 3 b. 2 and 3 iii. How will you calculate reaction
c. 1 and 4 d. 2,3 and 4 enthalpy from data on bond
enthalpies?
ix. For vaporization of water at 1 bar,
iv. What is the standard enthalpy of
∆H = 40.63 kJ mol-1 and ∆S = 108.8 combustion ? Give an example.
J K-1 mol-1. At what temperature,
∆G = 0 ? v. What is the enthalpy of atomization?
Give an example.
a. 273.4 K b. 393.4 K
vi. Obtain the expression for work done
c. 373.4 K d. 293.4 K in chemical reaction.
87
vii. Derive the expression for PV work ix. Calculate standard enthalpy of reaction,
viii. What are intensive properties? Fe2O3(s) + 3CO(g) 2 Fe(s) + 3CO2(g),
Explain why density is intensive from the following data.
property. ∆fH0(Fe2O3) = -824 kJ/mol,
ix. How much heat is evolved when 12 g ∆fH0(CO) = -110 kJ/mol,
of CO reacts with NO2 ? The reaction
is : ∆fH0(CO2) = -393 kJ/mol
Ans. : (-25 kJ)
4 CO(g) + 2 NO2(g)
x. For a certain reaction ∆H0 =219 kJ and
4 CO2(g) + N2(g), ∆rH0 = -1200 kJ ∆S0 = -21 J/K. Determine whether the
4. Answer the following questions. reaction is spontaneous or nonspontaneous.
i. Derive the expression for the maximum xi. Determine whether the following reaction
work. is spontaneous under standard state
conditions.
ii. Obtain the relatioship between ∆H and ∆U
for gas phase reactions. 2 H2O(l) + O2(g) 2H2O2(l)
iii.
State Hess’s law of constant heat if ∆H = 196 kJ, ∆S = -126 J/K
0 0
v. Obtain the relation between ∆G and ∆Stotal How much PV work is done?
Comment on spontaneity of the reaction. Ans. : (-69.8 kJ, 2.48 kJ)
vi. One mole of an ideal gas is compressed xiii. Calculate the work done during synthesis
from 500 cm3 against a constant external of NH3 in which volume changes from
pressure of 1.2 × 105 Pa. The work involved 8.0 dm3 to 4.0 dm3 at a constant external
in the process is 36.0 J. Calculate the final pressure of 43 bar. In what direction the
volume. (200 cm3) work energy flows?
vii. Calculate the maximum work when 24 Ans. : (17.2 kJ, work energy flows into
g of O2 are expanded isothermally and system)
reversibly from the pressure of 1.6 bar to xiv. Calculate the amount of work done in the
1 bar at 298 K. (a) oxidation of 1 mole HCl(g) at 200 0C
Ans. : (-873.4 J) according to reaction.
viii. Calculate the work done in the 4HCl(g) + O2(g) 2 Cl2(g) + 2 H2O(g)
decomposition of 132 g of NH4NO3 at (b) decomposition of one mole of NO at
100 0C. 300 0C for the reaction
NH4NO3(s) N2O(g) + 2 H2O(g) 2 NO(g) N2(g) + O2
State whether work is done on the system Ans. : (a = + 983 kJ ; b = 0 kJ)
or by the system.
Ans. : (-18.6 kJ)
88
xv. When 6.0 g of O2 reacts with CIF as per is -620 J when 100 ml of ethylene and 100
2Cl F(g) + O2(g) Cl2O(g) + OF2(g) mL of H2 react at 1 bar pressure. Calculate
the pressure volume type of work and ∆U
The enthalpy change is 38.55 kJ. What is for the reaction.
standard enthalpy of the reaction ?
Ans.: (W = +10.13 J; ∆U = -609.9 J)
(∆rH0 = 205.6 kJ)
xx. Calculate the work done and comment
xvi. Calculate the standard enthalpy of on whether work is done on or by the
formation of CH3OH(l) from the following system for the decomposition of 2 moles of
data NH4NO3 at 100 0C
3
i.CH3OH(l)+ O2(g) NH4NO3(s) N2O(g) + 2H2O(g)
2
CO2(g)+ 2H2O(l), Ans. (-18.61 kJ, work is done by the system)
∆H0 = -726 kJ mol-1
ii. C (Graphite) + O2(g) CO2(g), Activity :
∆cH = -393 kJ mol
0 -1
Following are some processes
1 occurrring in nature.
iii. H2(g) + O2(g) H2O(l),
2 • River originates in a mountain and
∆fH0 = -286 kJ mol-1
flows towards sea.
Ans. : (- 239 kJ mol-1) • After proper incubations for 21 days
xvii. Calculate ∆H for the following reaction
0 a chicken egg hatches and baby chick
at 298 K comes out.
H2B4O7(s) + H2O(l) 4HBO2 (aq) • List out some more processes you
come across in nature.
i. 2H3BO3(aq) B2O3(s) + 3H2O(l),
• Identify the processes that are in
∆H0 = 14.4 kJ mol-1 accordance with the second law of
ii. H3BO3(aq) HBO2(aq) + H2O,(l) thermodynamics and those which
∆H0 = -0.02 kJ mol-1 are against it.
89
5. ELECTROCHEMISTRY
makes possible the manufacture of essential
Can you recall ? chemicals. You have learnt preparation of
• What is a redox reaction ? NaOH, widely used in the manufacture of
• Which form of energy is soaps, detergents and paper, by electrolysis of
converted into electrical energy in dry NaCl. Electrolysis is possibly the only means
cells ? to produce fluorine. The processes such as
electro-refining (for purification of metals),
electroplating (for coating one metal is on the
surface of another) are also electrochemical
processes.
In standard XI, you learnt redox reactions.
Redox reaction forms the basis for the
• How is NaOH manufactured from generation of electricity by chemical reactions
NaCl ? and also for chemical reactions brought out
by means of electricity. These processes
5.1 Introduction : Dry cell is used to power are carried out in an electrochemical cell.
our electrical and electronic equipments Electrochemistry deals with the design and
because it generates electricity. Do you operation of such cells.
know how does a dry cell generate electricity
? A chemical reaction occurs in it which The current research in electrochemistry
generates electricity. Thus in a dry cell is focused on the design of fuel cells. The
chemical energy is converted into electrical fuel cells are being explored as convenient
energy. and compact source of electricity.
You are familiar with the electrolysis 5.2 Electric conduction : We know that the
of solutions of ions. Electrolysis is breaking electric current represents a charge transfer.
down of an ionic compound by the passage A charge transfer or flow of electricity occurs
of eletricity. Breaking down of an electrolyte through substances called conductors. There
during electrolysis is a chemical reaction are two types of conductors which give rise
that takes place by the passage of electricity. to two types of conduction of electricity.
Electrical energy is, thus, converted into 5.2.1 Metallic conduction :
chemical energy.
Can you recall ?
Electrochemistry is the area of chemistry
• What is the origin of electrical
which is concerned with interconversion of
conductivity of metals ?
chemical and electrical energy.
It also deals with the resistance and Electrical conduction through metals
conductance of aqueous electrolytic solutions. involves a direct flow of electrons from one
The determination of conductivities of aqueous point to the other. The outermost electrons of
electrolytic solutions provide an information metals form conduction bond. The electrons in
on the extent of ionization of electrolytes in conduction band are free to move and hence
water. (Refer to Chapter 3). flow under the influence of applied electrical
potential (Chapter 1). Metallic conductors
The study of electrochemical cells is
are, thus, electronic conductors.
important in science and technology. It
90