1.

(i)
Effect of Temperature on Heat of Reaction: The Kirchhoff Equation

The heat change accompanying chemical or physical processes generally depends on the
temperature at which the process takes place. This dependence is mathematically expressed in the
form of what is known as Kirchhoff equation after G. R. Kirchhoff (1858) who first developed this
equation. The equation may easily be derived with the help of the first law of thermodynamics.

Consider the process in which the reactants in state A at temperature T1 are converted into products in
state B a temperature T2. Assume that all operations are carried out at constant pressure. The
conversion may be carried out in two ways but according to Hess’s law the total heat change must be
the same in both cases.

(1) The reactants in state A at temperature T1 are heated to a temperature T2. The heat absorbed is
(∆T) (CP)A. where ∆T = T2 – T1, and (CP)A is the heat capacity of the reactants in the state A. The
reaction is now allowed to take place at this temperature and the heat change for the process is (H B –
HA)2 = ∆H2

The total heat change for the process = (∆T) (CP)A + ∆H2.

(2) The reactants in state A at temperature T1 are considered to products in state B at the same
temperature. The heat cement change = (HB – HA)1 = ∆H1. The temperature of the products is then
raised from T1 to T2 and the heat absorbed is (∆T) (CP)B, where (CP)B is the heat capacity of the
products.

The total heat change for the process = (∆T) (CP)B + ∆H1.

From Hess’s law,

(∆T) (CP)A + ∆H2 = (∆T) (CP)B + ∆H1

or, ∆H2 – ∆H1 = [(CP)B – (CP)A] x (∆T)

= ∆CP (∆T)

where, ∆CP = (CP)B – (CP)A

or, [∆H2 – ∆H1] / ∆T = ∆CP

For an infinitesimally small change in temperature one can write,

[d∆H / dT] = ∆CP … … … … (1)

Similarly, it may be shown that if the process is carried out at constant volume the relationship is;

[d∆U / dT] = ∆C … … … … (2)

The relationships (1) and (2) are different forms of the Kirchhoff equation. The equations are useful for
calculating the heat 41 reaction at a given temperature when the value is known at another
temperature provided the heat capacities of the reactants and products are also known.
Adiabatic Temp

In thermodynamics, an adiabatic process is one that occurs without transfer of heat or matter between
a thermodynamic system and its surroundings. In an adiabatic process, energy is transferred to its surroundings
only as work.[1][2] The adiabatic process provides a rigorous conceptual basis for the theory used to expound the first
law of thermodynamics, and as such it is a key concept in thermodynamics.
Some chemical and physical processes occur so rapidly that they may be conveniently described by the term
"adiabatic approximation", meaning that there is not enough time for the transfer of energy as heat to take place to
or from the system.[3]
By way of example, the adiabatic flame temperature is an idealization that uses the "adiabatic approximation" so as
to provide an upper limit calculation of temperatures produced by combustion of a fuel. The adiabatic flame
temperature is the temperature that would be achieved by a flame if the process of combustion took place in the
absence of heat loss to the surroundings.
A process that does not involve the transfer of heat or matter into or out of a system, so that Q = 0, is
called an adiabatic process, and such a system is said to be adiabatically isolated. [4][5] The assumption that a
process is adiabatic is a frequently made simplifying assumption. For example, the compression of a gas
within a cylinder of an engine is assumed to occur so rapidly that on the time scale of the compression
process, little of the system's energy can be transferred out as heat to the surroundings. Even though the
cylinders are not insulated and are quite conductive, that process is idealized to be adiabatic. The same can
be said to be true for the expansion process of such a system.
The assumption of adiabatic isolation of a system is a useful one, and is often combined with others so as
to make the calculation of the system's behaviour possible. Such assumptions are idealizations. The
behaviour of actual machines deviates from these idealizations, but the assumption of such "perfect"
behaviour provide a useful first approximation of how the real world works. According to Laplace, when
sound travels in a gas, there is no time for heat conduction in the medium and so the propagation of sound
is adiabatic. For such an adiabatic process, the modulus of elasticity (Young's modulus) can be expressed
as E = γP, where γ is the ratio of specific heats at constant pressure and at constant volume (γ = Cp/Cv )
and P is the pressure of the gas

HUMIDITY
Humidification is the process of constituting the water-vapor content in a gas. The reverse of the operation
is called dehumidification. Both are important for many industrial operations such as air conditioning, gas
cooling, controlled drying of wet solids, comfort heating etc. When a gas is brought in contact with a pure
liquid in which it is essentially insoluble, interphase mass and heat transfer takes place [1-3].
Four major applications of humidification operations are as follows:
a) Humidification of gases for controlled drying of wet solids
b) Dehumidification and cooling of gas in air conditioning
c) Gas cooling with the help of water
d) Cooling of liquid (e.g. water) before reuse
Air, for the purpose of this discussion, is defi ned as a gaseous mixture of nitrogen, oxygen, carbon dioxide, water
vapor (humidity), several inert gases, and traces of ozone and submicroscopic solid matter, sometimes called
permanent atmospheric substances. All other airborne substances are considered contaminants. The water vapor
(humidity), being a gas, occupies space along with the other gases of the air. In HVAC engineering, air is considered
as being made up of only two components-dry air and water vapor. The properties of the dry air, composed of
nitrogen, oxygen, carbon dioxide and rare gases, remain relatively unchanged as the temperature of the air rises and
falls. The water vapor, on the other hand, may undergo considerable alteration as the temperature changes,
including changes of state (condensing and freezing). Substantial amounts of energy are involved in these
transformations. In measuring these changes, and when working with the processing of air for various air
conditioning problems, the engineer is concerned with two basic lawsThermodynamics and Psychrometry.
Thermodynamics is the study of heat energy transformations and substances which are affected by them.
Psychrometry deals with the measurement of atmospheric conditions, particularly the moisture mixed with air
A psychrometric chart is a graphic representation of the thermodynamic tables which the HVAC engineer fi nds
convenient to use when plotting solutions for the various air conditioning processes involving water vapor and
temperature changes.

Enthalpy of Humid Air

Moist air is a mixture of dry air and water vapor. In atmospheric air water vapor content varies from 0 -
3% by mass. The enthalpy of moist and humid air includes the

 enthalpy of the dry air - the sensible heat

  enthalpy of the evaporated water in the air - the latent heat
The total enthalpy - sensible and latent - is used when calculating cooling and heating processes.

Specific enthalpy - h - (J/kg, Btu/lb) of moist air is defined as the total enthalpy (J, Btu) of the dry air and the
water vapor mixture - per unit mass (kg, lb) of dry air.

Specific Enthalpy of Moist Air

Specific enthalpy of moist air can be expressed as:

h = h a + x hw (1)

where

h = specific enthalpy of moist air (kJ/kg, Btu/lb)

ha = specific enthalpy of dry air (kJ/kg, Btu/lb)

x = humidity ratio (kg/kg, lb/lb)

hw = specific enthalpy of water vapor (kJ/kg, Btu/lb)

Example - Enthalpy in Moist Air

The enthalpy of humid air at 25oC with specific moisture content x = 0.0203 kg/kg (saturation), can be
calculated as:

h = (1.006 kJ/kgoC) (25oC) + (0.0203 kg/kg) [(1.84 kJ/kgoC) (25oC) + (2501 kJ/kg)]

= (25.15 kJ/kg) + [(0.93 kJ/kg) + (50.77 kJ/kg)]

= 76.9 (kJ/kg)

Note! - the latent heat due to evaporation of water is the major part of the enthalpy. The sensible heat due
to heating evaporated water vapor can be almost neglected.