Lecture

Thermo I
 Temperature dependance of
heat capacity
• The temperature dependence of heat
capacity are given by an empirical
equation;thetwo simplest
expressions of practical values are
• Cp /R=α+βT+γT2 and Cp /R=
a+bT+cT-2
• And by combining these we can
write
• Cp /R= A+BT+ CT2+DT-2 where one
from C or D is zero.
• Here Cp is the ideal
gas heat capacity.
• Real gases become
ideal in the limit
P→0
• Gases in the ideal
states have
properties that
reflect their
indivisuality as
does real gases
• Ideal gas heat
capacities are
different for
different gases
although functions
• Ideal gas heat capacities increases
with increase in temperature
• Values of different parameters A,B,C
can be found from elsewhere and
from the end of our text book
• Gas mixtures are treated in exactly
the same way as that of pure gases
• As in ideal gases the molecules have
no influence on one another
• This means each gas exists in a
mixture independent of the
others;its properties are uneffected
by the presence of other molecules
• Thus heat capacity of the mixture
can be calculated as the weighted
sum of the indivisual heat
capacities
• The molar heat capacity of the
gaseous mixture in the ideal state
can be expresses as
• Cp (mixture)= yA CpA ig + yB CpB ig + yC
CpC ig
• The values of heat capacities can
similarly be found for solids or
liquids and the values of their
parameters can also be found form
App C
Evaluation of Sensible heat
integral
Use of defined Functions
 Latent heats of pure
substances
• In this heat the characteristics feature
of all the processes is the coexistence
of two phases. According to the phase
rule a two phase system consisting of
a single species is univariant and its
intensive state can be defined by the
specification of just one intensive
property.
• Thus heat capacity is a function of
temperature only and is related to the
other properties by an exact
• ∆H= T ∆V dPsat /dT
• ∆H=Latent heat
• ∆V= volume changes accompanying
the phase change
• Psat =vapour pressure
• When this equation is applied to the
vaporization of a pure liquid dPsat
/dT is the slope of vapour pressure
vs temperature curve at a
temperature of interest
• ∆V is the volume changes between
the saturated vapor and the
saturated liquid and ∆H is the
latent heat of vapourization.Thus
∆H can be calculated from vapor
pressure and the volumetric data.
• Latent heats may also be measured
calorimetrically.
• Experimental values are available at
selected temperatures for many
substances
• Approximate methods are used when
the data is not available for latent
heat calculations
• Alternate methods serve one of these
two purposes
ü Prediction of heat of vaporization at
normal boiling point i.e., at a pressure
of 1 standard atmosphere
ü Estimation of heat of vaporization at
any temperature from the known
value at a single temperature
• Rough estimates of latent heats of
vaporization for pure liquids at their
normal boiling points are given by
Trouton’s rule
• ∆Hn /RTn ≈ 10
• Where Tn is the absolute temperature
of the normal boiling point.The
units of the ∆Hn R,Tn must be
chosen so that ∆Hn /RTn is the
dimensionless.
Standard Heat of Reaction