Phase Diagram

Map showing ranges of T

and p over which various
phases are stable.
Phase BoundariesMelting, Vaporization and
Boiling Curves
Triple Point, Critical Point
Phase Rule F = C P + 2

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Clapeyron equation
The slopes of the lines of two phase equilibrium in the p-T
phase diagrams are related to the entropy change and volume
change.
Gm(T,p) = Gm(T,p)

For equilibrium of phases and at T and p. Suppose p is

changed to p + dp, and T to T + dT, and equilibrium is to be
maintained, then require dGm(T,p) = dGm(T,p)
Sm dT + Vm dp = Sm dT+ Vm dp
Rearranging, dp/dT = (Sm Sm) /(Vm Vm = transS/transV

Using transS = transH/T, can rewrite the equation as

dp/dT = transH/T(transV)
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Clausius Clapeyron equation

For solid-gas equilibrium or liquid-gas equilibrium away
from the critical point.

Vmg Vml Vmg RT/p

dp/dT vapH/TVmg vapHp/RT2

or d(ln p)/dT = vapH/RT2 which is the ClausiusClapeyron equation. Over small ranges of temperature,
this may be integrated assuming constant vapH yielding
ln (p2/p1) = (vapH/R)(1/T2 1/T1)

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Chemical potential and composition

For a perfect gas, Gm(T,p) = Gm0(T) + RT ln(p/p0), where
Gm0(T) is the standard molar Gibbs energy at the given T
and p0 = 1 bar.
In a perfect gas mixture, i(T,p,x) = i0(T) + RT ln(pi/p0)
where pi is the partial pressure of constituent i, and i0 = Gmi0
For any solutions which are very dilute in the solutes
i(T,p,x) = i0(T) + RT ln[i], where [i] is the molar
concentration.

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Chemical Reactions
As with physical processes, the heat transfer
accompanying chemical reactions at a given
temperature are also measured usually under
conditions of constant volume or constant pressure.
At constant volume, qV = (U)V U
At constant pressure, qp = ()p H
H = U + (pV) U + gasRT where gas is the
difference (products reactants) in the sum of the
stoichiometric coefficients of gas phase species.

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Standard states
Reaction enthalpies are usually reported for a set of so
called standard conditions at a given temperature. The
standard state of a substance is the pure substance in the
specified physical state of aggregation, ie., gas, liquid or
solid, and the particular crystalline modification eg.,
graphite/diamond, rhombic/ monoclinic sulfur, at the given
temperature and a pressure of 1 bar.

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Standard reaction enthalpies

For example, for the reaction
CH2=CH2(g) + H2(g) CH3-CH3(g), the standard enthalpy
change = 137 kJ at 298.15 K.
Similarly, for 2H2(g) + O2(g) 2H2O(l), 298 = 572 kJ.
Combustion Reaction:
CH4(g) + 2O2(g)CO2(g) + 2H2O(l), = -890 kJ
Standard enthalpy of combustion C298(CH4,g) is 890
kJ/mole

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Hess law
The standard enthalpy of a reaction is the sum of the
standard enthalpies of the reactions into which the overall
reaction may be divided. Example:
C3H6(g) + H2(g) C3H8(g) r1 = 124 kJ
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l)
r2 = 2220 kJ
H2O(l) H2(g) + O2(g) r3 = 286 kJ

C3H6(g) + (9/2) O2(g) 3CO2(g) + 3H2O(l)

r = r1 + r2 + r3 = 2058 kJ

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Standard enthalpy of formation

The standard enthalpy of formation of a substance is defined
as the standard enthalpy of the reaction leading to the
formation of one mole of the substance from its elements in
their reference states, ie., the element in its most stable state
under the prevailing conditions.
Standard enthalpies of reaction can be obtained from
standard enthalpies of formation using
r = i fi (products) i fi (reactants)

H2(g) + O2(g) H2O(l)

f298 (H2O(l))= 286 kJ/mole

C(s,graphite) + O2(g) CO2(g)

kJ/mole

f298(CO2(g)) = 393.5

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Enthalpy of Reaction
For C6H6(l) + 15/2 O2(g) 6CO2(g) + 3H2O(l)
r = 6 f(CO2(g)) + 3 f(H2O(l))
f(C6H6(l)) 15/2 f(O2(g))
= 6x(393.5) + 3x(285.8) (49) (0) = 3268 kJ

The enthalpy of combustion of benzene liquid is therefore

3268 kJ/mole

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Reaction Gibbs Energy

For the general reaction aA + bB cC + dD, at given
T and p, at some arbitrary composition, the Reaction
Gibbs Energy is given as rG = cC + dD aA bB

Note slopes.
rG < 0 Spontaneous
rG > 0 Spontaneous
At equilibrium,
(G/n)T,peq = rG eq = 0
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rG and composition
Since J = J + RT ln [J] for each constituent,

rG = d(D + RT ln [D]) + c(C + RT ln [C])

a(A + RT ln [A]) b(B + RT ln [B})
rG = rG + RT ln {([C]c [D]d)/([A]a [B]b)}
rG = rG + RT ln Q
where rG is the standard Reaction Gibbs Energy and Q is
called the reaction quotient.
More generally, use activity in place of concentration

For gases commonly use partial pressure pJ in place of [J]

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Equilibrium Constant
At equilibrium, rG = 0, or
rG = RT ln Qeq = RT {([C]c [D]d)/([A]a [B]b)}eq
rG = RT ln K
The equilibrium constant is a function of the temperature
alone.

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Spontaneity
Reaction feasible if rG << 0, ie., K >> 1, and not so if rG
>> 0, ie., K << 1
Since rG = rH T rS
(a) If rH < 0 (exothermic) and rS > 0, then rG < 0 at all
T
(b) If rH < 0 (exothermic) and rS < 0, then rG < 0
for T < rH / rS
(c) If rH > 0 (endothermic) and rS > 0, then rG < 0
for T > rH / rS

(d) If rH > 0 (endothermic) and rS < 0, then rG < 0 at

no temperature
Of course, it is rG which will ultimately decide the
feasibility, with rG = RT ln(Q/K)
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Effect of T on K and rG0

From rG0 = RT ln K, one has
d(lnK)/dT = d/dT ( rG0/RT)
From ((G/T)/T) = G/T2 S/T = -H/T2
d(lnK)/dT = rH0/RT2

which is called vant Hoff equation. If assumed independent

of T, then
ln (K2/K1) = (rH0/R) (1/T1 - 1/T2)
Note le Chatelier principle

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Chemical Kinetics
How rapidly reactants are consumed and products formed

How reaction rates respond to changes in conditions such

as temperature and pressure, or the presence of a catalyst
Practical importance of predicting speed of reaction and
approach to equilibrium.
Leads to an understanding of reaction mechanism, the
analysis of a reaction into a sequence of elementary steps

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Reaction Rate
Raw Data:
Concentrations of reactants/
products at series of times after
reaction started.
Information, especially structural, on
any intermediate
Instantaneous rate is proportional to
the slope of the graph of
concentration versus time
Consider the reaction N2(g) + 3H2(g) 2NH3(g)
Rate = d[N2]/dt = 1/3 d[H2]/dt = d[NH3]/dt

If at some time rate of formation of NH3 is 1.2 mmol l-1 s-1,

then rate of consumption of N2 is 0.6 mmol l-1s-1
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Differential Rate Law

Equation that represents the rate of reaction in terms of
the molar concentrations of the species in the overall
reaction (including, possibly the products).
Often found to be proportional to the molar concentrations
of the reactants raised to simple powers.

If the rate of aA + bB Products is of the form, Rate =

k[A]m[B]n, reaction said to be of order m in A, and order n in
B, and order m+n overall. k is called the rate constant,
characteristic of reaction
For example, for H2 + I2 2HI, d[H2]/dt = k[H2][I2]
Reaction is first order in H2, first order in I2 and second order
overall
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Rate Laws
NO2 + CO NO + CO2 , Under certain conditions,
d[CO]/dt = k[NO2]2 so that the reaction is second order in
NO2, zero order in CO, and order two overall
Rate Law may be more complicated and it may not always
be possible to specify order. For eg., for

H2 + Br2 2HBr
d[HBr]/dt = k[H2][Br2]3/2/{[Br2] + k[HBr]}
When k[HBr] << [Br2] this simplifies to
d[HBr]/dt = k[H2][Br2]1/2
The order with respect to a component may even be
negative
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Determination of rate law

Measurement of any convenient physical property, such as
pressure, density, absorbance, conductivity etc., or chemical
analysis may be used to follow the rate
Method of Initial Rates:
Instantaneous rate measured at beginning of reaction for
several different initial concentrations of reactants.
Often used in conjunction with Isolation Method.
If initial rate r0 = k[A]0n, then
ln r0 = ln k + n ln[A]0 so that a plot of lnr0 versus ln[A]0 has
slope n

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Example
2I(g) + Ar(g) I2(g) + Ar(g)
[I]0/M

1.0x10-5

2.0x10-5

4.0x10-5

6.0x10-5

[Ar]0/M

1.0x10-3

Rate/M s-1

8.70x10-4

Rate/M s-1

3.48x10-3

Rate/M s-1

1.39x10-2

Rate/M s-1

3.13x10-2

5.0x10-3

4.35x10-3

1.74x10-2

6.96x10-2

1.57x10-1

1.0x10-2

8.69x10-3

3.47x10-2

1.38x10-1

3.13x10-1
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Example

Slope = 2

Slope = 1

-(1/2)d[I]/dt = k[I]2[Ar]
By plotting the intercepts of the first graph versus
log[Ar]0, determine k = 8.6x109 l2mol-2s-1
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Integrated Rate Laws

Expression for the concentration of a species as a function
of time, which is what is experimentally measured typically.

First order reaction, say A P, with d[A]/dt = k[A]

Integrate from t = 0 when [A] = [A]0 to desired time t to find
ln[A] ln[A]0 = kt, so that a plot of ln[A] vs. t is linear with
slope = -k.
[A] = [A]0 ekt, and [P] = [A]0(1 ekt)
Similarly, for a reaction A Products with d[A]/dt = k[A]2,
one obtains
1/[A] = 1/[A]0 + kt so that a plot of 1/[A] versus t is a straight
line of slope k
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Half Life
Alternatively, for the second order reaction above,
[A] = [A]0/(1 + [A]0kt), and

[P] = kt([A]02)/(1 + kt[A]0)

The half-life t1/2 of a reactant is the time taken for its
concentration to fall to half the initial value
For a first order reaction, the half life of the reactant on
whose concentration the reaction rate depends is given by
t1/2 = (ln 2)/k, seen to be independent of [A]0.
For a reaction, say A P, with -d[A]/dt = k[A]2, the half life is
found to be t1/2 = 1/k[A]0
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