Steam

Enthalpy Calculations
 Steam

Objectives

 Retrieve enthalpy values using tables and charts

 Calculate enthalpy values using tabulated data
 Calculate enthalpy values using steam tables with no phase change
 Calculate enthalpy values using steam tables with phase change
FORMATION OF STEAM

Step 1:
Warming phase in which the temperature of the water increases up to the saturation temperature. The
energy required to produce this temperature rise is called the liquid enthalpy.

Step 2:
This takes place at constant temperature and is the stage during which the transformation from water
into steam takes place. At the beginning all the water is at the saturated temperature and at the end all
the dry saturated steam is at the saturated temperature. Between these two extremes, the steam formed
is always wet. The energy required to produce the total change from all water into all steam is called the
enthalpy of evaporation.

Step 3:
This phase begins when all the dry saturated steam has been formed at saturation temperature. Further
transfer of heat produces superheated steam, which is accompanied by a rise in temperature. The
amount of energy added is called the superheat enthalpy.
Wet Steam
Specific Enthalpy hx h f  xh fg kJ/kg
Specific Volume v x  xv g m3/kg
Specific Internal Energy u x hx  pv kJ/kg

Dry Saturated Steam

Specific Enthalpy hg h f  h fg

Specific Volume v g value in table

Specific Internal Energy u g hg  pv

Superheated Steam
Specific Enthalpy hsup h f  h fg  Cpt sup  t sat 

0.233hsup  1943
Specific Volume vsup 
p
Example 1

On temperature – enthalpy axis show what happens when:

(a) 1 kg of water initially at 00C is brought to the boil at 100kPa and converted to wet steam having
a dryness fraction of 0.9

(b) 1kg of water initially at 650C is converted to dry saturated steam at 350kPa

(c) 4 kg of superheated steam at 3000C and 2Mpa are formed from water initially at 720C (for
superheated steam Cp= 2.6kJ/kg.K).

In each case calculate the specific enthalpy/ change of specific enthalpy or change of enthalpy of
the steam formed.
Example 2

Determine how much heat is required to convert 6kg of water at a pressure of 680kPa and
temperature 150,3 0C to superheated steam having a temperature of 2000C at 680kPa (Cp = 2.46
kJ/kg.K). How much of the enthalpy of this superheated steam is stored as internal energy.
Student Tutorial Questions

Question 3
Question 1 What is the specific enthalpy of saturated
Determine the enthalpy (in kJ/kg) of liquid water water under the following conditions:
at the following temperatures: at 45OC
100OC at a pressure of 12,335 kPa
At 83OC
125OC At 90 kPa
18OC At 77 kPa

Question 2 Question 4
What is the temperature at which liquid water What is the enthalpy of water/vapour under
will have a specific volume of 0.0010199 m3/kg? the following conditions:
At what temperature will water vapour have a 100OC and 60kPa
specific volume of 1.035 m3/kg? 150OC and 50kPa
175OC and 50kPa
315OC and 740kPa
ENTHALPY CALCULATIONS
ENTHALPY CALCULATIONS
Phase Transitions:
Phase transitions occur from solid to liquid phase and from liquid to gaseous phase.
During the transition, large changes occurs in the enthalpy of the substance.

Latent heat – changes in enthalpy, which occurs as a result of a phase change, with no
notable change in temperature

For a single phase, the enthalpy varies as a function of temperature. (sensible heat
changes)

 Heat of fusion – changes in enthalpy for melting (∆Hfusion)

 Heat of vaporization – changes in enthalpy for vaporization (∆H vap)
 Heat of condensation – the negative of the heat of vaporization
 Heat of solidification – the negative of the heat of fusion
Heat of reaction is the change in enthalpy of the
system for the reaction proceeding at constant
temperature.
It is the difference between the enthalpy of
products and the enthalpy of reactants and is
denoted by ∆H.

Positive values of ∆H indicate increase in the

enthalpy and therefore represent endothermic
reactions.
Negative values of ∆H indicate decrease in
enthalpy and represent exothermic reactions.

STANDARD HEAT OF REACTION

The standard heat of reaction at a temperature T is the enthalpy change accompanying
a reaction when both the reactants and products are at their standard states at
temperature T.

It is represented by the symbol ∆HT0, the superscript ‘0’ indicates that the heat of reaction
refers to the standard conditions.

By convention, the standard heats of reaction are reported at a temperature of 298 K and
represented by ∆H2980.

The heat evolved or absorbed in a chemical reaction corresponds to the stoichiometric

numbers as written in the chemical equation.
The change in enthalpy accompanying the formation of 1 mol of a substance from the
constituent elements is termed the heat of formation.

When the reactants and products are at their standard states, the heat of formation is called
the standard heat of formation.

The standard heat of formation of carbon monoxide gas at 298 K, ∆H 0f,298 = -110.525 KJ/mol
(Table C.4 Smith, Van Ness & Abbott)

Similarly, if the data on the heat of formation of all the substances taking place in a chemical
reaction are available, the heat of reaction may be calculated as:
H 0   H 0
f 
Products
 H 0
f
Reactants
The standard heats of formation of elements are taken as zero.
STANDARD HEAT OF FORMATION
Example 3
a) Calculate the standard heat of reaction for the following reaction:
4HCl( g )  O2 ( g )  2 H 2O( g )  2Cl2 ( g )

b) Calculate the standard heat of formation of ammonia gas.

When the reaction under consideration is a combustion reaction, the heat of reaction is known as heat of
combustion (usually expressed per mole of substance reacted).

The negative of the heat of combustion of a fuel is referred to as its heating value or calorific value. This is
the energy exchanged with the surroundings when one unit mass of fuel is burnt in Oxygen.

The heat of combustion of a fuel is a negative quantity , whereas the heating value is positive.
When water formed during combustion is in liquid state, the energy liberated (Gross heating value) will be more
than the energy liberated when the combustion products contain water in the vapour state (Net heating value).

The Gross heating value is often referred to as the Higher Calorific Value (HCV).
[Water Products of combustion are in the liquid state]

The Net heating value is often referred to as the Lower Calorific Value (LCV).
[Water Products of combustion are in the vapour state]
STANDARD HEAT OF COMBUSTION
 The Standard Heat of Reaction at temperature T is:

0 H  H
H T 1 2  H 3

TEMPERATURE DEPENDENCE OF STANDARD HEATS

The heat capacity of the substance is represented by:
Cp   T  T 2

The following equation results which can be used for the

evaluation of the standard heat of reaction at any temperature T:

 2  3
HT0 H '  T  T  T
2 3
Enthalpy calculations using Heat Capacity Equations

The enthalpy change for a substance in a single phase can be calculated using the heat capacity.

If Cp is constant, the change in enthalpy will be Cp∆T

Heat capacity varies with temperature for solids, liquids and real gases, but it is a continuous
function of temperature only in the region between phase transitions.

Heat capacity
 change in internal energy (specific heat) at constant volume (C v)
 change in internal energy at constant pressure (C p)
 defined to be the amount of heat necessary to raise the temperature of one kg of
substance by one degree in a closed system, if the process is at constant volume
 SI units are J/kgK
Enthalpy change can be calculated by integrating the heat capacity equation
with respect to temperature in the following manner:
Example 4
For the following reaction the standard heat of reaction at 298 K is -164.987 kJ.

The heat capacity is given by: Cp    T  T 2

The constants in the heat capacity (J/mol.K) equation are given below:

α β γ
CO2 26.75 42.26x10-3 -14.25x10-6
H2 26.88 4.35 x10-3 -0.33 x10-6
H2O 29.16 14.49 x10-3 -2.02 x10-6
CH4 13.41 77.03 x10-3 -18.74 x10-6

Calculate the heat of reaction at 773K

Example 5:
Calculate the heat of reaction for the following reaction at 400K:

C6H5Cl + O2 → 6 CO2(g) + 2 H2O (g) + HCl(g)

The heat of formation, Hf (HCl) = - 92 312 kJ/kmol

 The latent heat of water is 40.600 kJ/mol

Question 2:
Calculate the heat of reaction for the
Student Tutorial following reaction at 400K:
C6H5Cl + O2→6 CO2(g) + 2 H2O (g)
Question 1 + HCl(g)

Calculate the standard heat of combustion of methane at The heat of formation, Hf (HCl) = -
533K and compare that to the standard heat of combustion
92 312 kJ/kmol
calculated at 298K. The products of combustion are CO 2(g)
and H2O(g).
Mean molar Standard Heat
heat capacities of Formation
kJ/mol.K kJ/mol

CH4 (g) 4.184 x 10-2 -74.520

O2(g) 3.305 x 10-2 0

CO2(g) 4.142 x 10-2 -393.509