Energy Balances

• Energy balance equation (1st Law)

• Enthalpy change

• Mass and energy balances for non-reacting systems

• Mass and energy balances for reacting systems

1
 Conservation of Energy for a Control Volume
ENERGY BALANCE FOR OPEN SYSTEMS
 time rate of change   net rate at which   net rate at which   net rate of energy 
 of the energy   energy is being   energy is being   transfer into the 
       
 contained within    transferred in    transferred out    control volume 
       
 the control volume at   by heat transfer   by work   accompanying 
 time t   at time t   at time t   mass flow 

dEcv     Vi 2    Ve2 
 Q  W  mi  ui   gzi  me  ue   gze 
dt  2   2 

Which for steady state is given by

   Vi 2    Ve2 
0  Qcv  Wcv   mi  hi   gzi    me  he   gze 
i  2  e  2  2
 Nozzles and Diffusers

Common Form of 1st Law:

   Vi 2    Ve2 
0  Qcv  Wcv   mi  hi   gzi    me  he   gze 
i  2  e  2 

 V12  V22 
0   h1  h2    
 2  3
 Compressors and Pumps

Rotating compressors
Reciprocating compressor

Common Form of 1st Law:

  
 Vi 2    Ve2 
0  Qcv  Wcv   mi  hi   gzi    me  he   gze 
i  2  e  2 

W  V12  V22 

  h1  h2      g  z1  z2 
m  2  4
 Heat Exchangers
Tube-within-
a-tube
Direct Contact counterflow

Tube-within- Cross-flow
a-tube
parallel flow

Common Form of 1st Law:

   Vi 2    Ve2 
0  Qcv  Wcv   mi  hi   gzi    me  he   gze 
i  2  e  2 

  Vi 2    Ve2 
i mi  hi  2  gzi   e me  he  2  gze 
   
5
 Turbines

Common Form of 1st Law:

   Vi 2    Ve2 
0  Qcv  Wcv   mi  hi   gzi    me  he   gze 
i  2  e  2 

W  V12  V22 

  h1  h2      g  z1  z2 
m  2 
6
 Energy balance Equation
Example
Water flows through the system shown below at a rate of 20 L/min.
Estimate the pressure required at point 1 if friction losses are negligible.

7
Example …. continued
Assumptions/simplifications
No heat transfer
No work,
Steady state
Isothermal
The above equation reduces to: 𝑉𝑒2 − 𝑉𝑖2
𝑝𝑒 𝑣𝑒 − 𝑝𝑖 𝑣𝑖 + + 𝑔 𝑧𝑒 − 𝑧𝑖 = 0
2
Δ𝑃 Δ𝑉 2
+ + 𝑔Δ𝑧 = 0 The Bernoulli equation
𝜌 2

8
 Conservation of Energy for a Control Volume

Which for steady state is given by

  
 Vi 2    Ve2 
0  Qcv  Wcv   mi  hi   gzi    me  he   gze 
i  2  e  2 
For most chemical engineering applications, we ignore KE and PE
𝑑𝐸 𝑑𝑈
= = 𝑄−𝑊+ 𝑚𝑖𝑛 ℎ𝑖𝑛 − 𝑚𝑜𝑢𝑡 ℎ𝑜𝑢𝑡
𝑑𝑡 𝑑𝑡
Which for steady state is given by 0 = 𝑄 − 𝑊 + 𝑚𝑖𝑛 ℎ𝑖𝑛 − 𝑚𝑜𝑢𝑡 ℎ𝑜𝑢𝑡

And is usually written as: 0= 𝑄−𝑊+ 𝑚𝑖𝑛 𝐻𝑖𝑛 − 𝑚𝑜𝑢𝑡 𝐻𝑜𝑢𝑡

Our focus will be on how to determine enthalpy values 9

 Calculation of Enthalpy and Enthalpy Change
Where can you get values of enthalpies or data to calculate enthalpy values?
Here are some sources:
1. Heat capacity and other equations
2. Equations to estimate the enthalpy of a phase transition
3. Tables (e.g. steam tables)
4. Enthalpy charts
5. Computer databases

Enthalpies can also be estimated by generalized methods based on the theory of

corresponding states or additive bond contributions; these will be addressed in
next year’s thermodynamics course
Enthalpy has no absolute value; only changes in enthalpy can be calculated.
A reference set of conditions is often used in computing enthalpy changes.
What’s the reference condition for steam tables
Liquid water at 0°C (32°F). This does not mean that the enthalpy is actually zero under
these conditions but merely that the enthalpy has arbitrarily been assigned a value of
zero at these conditions.
In computing enthalpy changes, the reference conditions cancel out (see next slide)
10
 Calculation of Enthalpy and enthalpy change
Initial state of the system (1) Final state of the system (2)

𝑠𝑝𝑒𝑐𝑓𝑖𝑐 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 = 𝐻1 − 𝐻𝑟𝑒𝑓 𝑠𝑝𝑒𝑐𝑓𝑖𝑐 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 = 𝐻2 − 𝐻𝑟𝑒𝑓

𝑁𝑒𝑡 𝑠𝑝𝑒𝑐𝑓𝑖𝑐 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑐ℎ𝑎𝑛𝑔𝑒 = 𝐻2 − 𝐻𝑟𝑒𝑓 − 𝐻1 − 𝐻𝑟𝑒𝑓

= 𝐻2 − 𝐻1

Will the enthalpy change be greater along the path shown by the solid line or the
path shown by the dashed line

11
 Point and Path Functions

1 and 2 represent different states. Also, A, B,

and C represent separate processes that may be taken
from state 1 to state 2. The lines corresponding to A, B,
and C may be considered the paths that correspond to
each process. The area under a curve, that is, of a–1–2–
b–a, depends on the path that is chosen.

An inexact differential or imperfect differential (or path function) is any quantity, such as heat,
Q, and work, W, that are not state functions. State function is a property of a system that
depends only on the current state of the system, not on the way in which the system acquired
that state (e.g. internal energy, U, and enthalpy, H). The symbol, δ indicates that Q and W are
path dependent while the symbol d denotes an exact, or path-independent, differential.

12
 Calculation of Enthalpy Change
Suppose, for example, that we wish to calculate the change in enthalpy for a process
in which solid phenol (C6H6O) at 25°C and 1 atm is converted to phenol vapor at 300
°C and 3 atm. If we had a table of enthalpies for phenol, we could simply subtract the
enthalpy at the initial state from the enthalpy at the final state.

What if we do not have tables?

Construct a hypothetical process path from the solid at 25°C and 1 atm to the vapor
at 300°C and 3 atm.

13
Property Diagrams: P-T (Multi-phase)

Solid
Liquid

3 atm State 2

1 atm State 1

Vapour

14

25 300
Temperature
Enthalpy Change (Across Phases)

This is at constant pressure

15
 Calculation of Enthalpy Change
Suppose, that we wish to calculate the change in enthalpy for a process
in which 1 mol/s of liquid benzene is heated and evaporated from an
inlet temperature and pressure of 20°C and 10 MPa respectively to an
outlet temperature and pressure of 200 °C and 1 bar respectively.

16
 Example Problem: Benzene

10,000 State 1

ΔH

ΔH1

ΔHvap
100
ΔH2 ΔH3
State 2

17
20 80 200
Temperature
 Calculation of Enthalpy Change
Suppose, that we wish to calculate the change in enthalpy for a process
in which 1 mol/s of liquid benzene is heated and evaporated from an
inlet temperature and pressure of 20°C and 10 MPa respectively to an
outlet temperature and pressure of 200 °C and 1 bar respectively.

𝑸 = 𝒏∆𝑯
𝑸 = 𝒏(∆𝑯𝟏 + ∆𝑯𝟐 + ∆𝑯𝒗𝒂𝒑 + ∆𝑯𝟑 )

∆𝑯𝟏 = 𝑫𝒆𝒑𝒓𝒆𝒔𝒔𝒖𝒓𝒊𝒛𝒂𝒕𝒊𝒐𝒏 𝒄𝒉𝒂𝒏𝒈𝒆 𝒊𝒏 𝑷

∆𝑯𝟐 = 𝑯𝒆𝒂𝒕𝒊𝒏𝒈 𝒂 𝒍𝒊𝒒𝒖𝒊𝒅 (𝒄𝒉𝒂𝒏𝒈𝒆 𝒊𝒏 𝑻)
∆𝑯𝒗𝒂𝒑 = 𝑽𝒂𝒑𝒐𝒓𝒊𝒛𝒂𝒕𝒊𝒐𝒏 𝒄𝒉𝒂𝒏𝒈𝒆 𝒊𝒏 𝒑𝒉𝒂𝒔𝒆
∆𝑯𝟑 = 𝑯𝒆𝒂𝒕𝒊𝒏𝒈 𝒂 𝒗𝒂𝒑𝒐𝒓 (𝒄𝒉𝒂𝒏𝒈𝒆 𝒊𝒏 𝑻)
How do you determine each of the ΔHs above?
18
 Calculation of Enthalpy Change
Suppose, that we wish to calculate the change in enthalpy for a process
in which 1 mol/s of liquid benzene is heated and evaporated from an
inlet temperature and pressure of 20°C and 10 MPa respectively to an
outlet temperature and pressure of 200 °C and 1 bar respectively.
In general, remember: 𝑯 = 𝑼 + 𝑷𝑽
∆𝑯 = ∆𝑼 + ∆(𝑷𝑽)
∆𝑯 = ∆𝑼 + 𝑽∆𝑷 + 𝑷∆𝑽
At constant temperature ΔU = 0, and for solids/liquids, the assumption
of incompressibility (or/and for a control volume) leads to PΔV =0
Therefore: ∆𝑯 = 𝑽∆𝑷

∆𝑯𝟏 = 𝑽∆𝑷 = 𝟎. 𝟎𝟖𝟖𝟖 ∗ 𝟏𝟎𝟓 − 𝟏𝟎𝟕 = −𝟖𝟖𝟎 𝑱/𝒎𝒐𝒍

19
 Calculation of Enthalpy Change
Suppose, that we wish to calculate the change in enthalpy for a process
in which 1 mol/s of liquid benzene is heated and evaporated from an
inlet temperature and pressure of 20°C and 10 MPa respectively to an
outlet temperature and pressure of 200 °C and 1 bar respectively.
In general, for sensible (single phase) Heating/cooling:
𝒅𝑯
= 𝑪𝒑 𝒅𝑯 = 𝑪𝒑𝒅𝑻
At constant Cp:
∆𝑯 = 𝑪𝒑∆𝑻 𝒅𝑻
∆𝑯𝟐 = 𝟖, 𝟑𝟖𝟎 𝑱/𝒎𝒐𝒍
∆𝑯𝒗𝒂𝒑 𝒂𝒕 𝟏 𝒃𝒂𝒓 = 𝟑𝟎, 𝟕𝟕𝟎 𝑱/𝒎𝒐𝒍
∆𝑯𝟑 = 𝟏𝟑, 𝟖𝟎𝟎 𝑱/𝒎𝒐𝒍
𝑸 = 𝟏 ∗ (−𝟖𝟖𝟎 + 𝟖, 𝟑𝟖𝟎 + 𝟑𝟎, 𝟕𝟕𝟎 + 𝟏𝟑, 𝟖𝟎𝟎)
𝑸 = 𝟓𝟐. 𝟏 𝒌𝑾 20
 Enthalpy Change
(Heat of Vaporization/Latent Heat/hfg)

Enthalpy

H(vapour at T1)

H(liquid at T1) Does the heat of vaporization vary with

Temperatures/Pressure or does it remain
constant?

T1 Temperature Tc

21
Determination of Heat Capacities (pure components)
1. Using the temperature Dependence of the Heat Capacity (empirical
equations derived by fitting experimental data)

where the (Cp/R) term is dimensionless and either C or D is zero, depending on the
substance considered.
The equation above can be used for liquids and solids

2. Average values may be used; i.e. evaluate Cp at T1 and Cp at T2

and use the average value (not recommended, unless the
temperature range is small)
3. Employing Charts
4. Computer or published Data bases (Perry & Green)
Ideal-gas heat capacities are different for different gases; although
functions of temperature, they are independent of pressure.
22
 Determination of Heat Capacities
Ideal-gas heat capacities increase
smoothly with increasing temperature
toward an upper limit, which is reached
when all translational, rotational, and
vibrational modes of molecular
motion are fully excited.

Temperature dependence is expressed

analytically by equations similar to the
equation below:

23
Heat Capacity Equations (pure components)

24
 Determination of Heat Capacities (mixtures/Solutions)
Ideal gas mixtures of constant composition may be treated in exactly the same way as pure
gases.
An ideal gas, by definition, is a gas whose molecules have no influence on one another. This
means that each gas in a mixture exists independent of the others; its properties are unaffected
by the presence of different molecules.
Thus one calculates the ideal-gas heat capacity of a gas mixture as the mole-fraction-weighted
sum of the heat capacities of the individual species.
The molar heat capacity of the mixture in the ideal-gas state is:

For a mixture of ideal gases or ideal liquids the total enthalpy change can be estimated as the
sum of the enthalpy changes for the pure mixture compounds; note that in reality you are
neglecting the enthalpy changes associated with the mixing of components; nevertheless this
rule is a very good approximation for mixtures of gases and for mixtures of similar liquids:

Where yi is the mass (or mole)

fraction of the ith component in The above equations are valid to the extent
the mixture. that enthalpies of mixing may be neglected.
25
 Latent Heat (pure components)
When a pure substance is liquefied from the solid state or vaporized from the liquid at constant
pressure, no change in temperature occurs; however, the process requires the transfer of a finite
amount of heat to the substance.

The characteristic feature of all these 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 is determined by the specification of just one intensive property.

Thus the latent heat accompanying a phase change is a function of temperature only, and is
related to other system properties by an exact thermodynamic equation:

The derivation of the above equation, known as the Clapeyron equation, will be
carried out in CHEN 314.

Simplification of this equation leads to the Clausis-

Clapeyron Equation:
26
 Latent Heat (pure components)
Rough estimates of latent heats of vaporization for pure liquids at their normal boiling points
are given by Trouton's rule:

Where Tb is the normal boiling point in K and the latent heat of vapourisation is in kJ/mol. This
rule has a very low accuracy, approximately 30%.
More accurate equations and correlations, such as the Clausius-Clapeyron equation detailed
previously, the Chen Equation, and the Riedel equation with an accuracy of 2% for a large
number of substances are given below:

Chen

Riedel

Where the critical and boiling point temperatures are in K and the critical pressures are in atm.
Estimates of the latent heat of vaporization of a pure liquid
at any temperature from the known value at a single
temperature may be based on a known experimental value
or on a value estimated by one of the previous equations.
The method proposed by Watson has found wide 27
acceptance:
 Mass and Energy Balances
Most of the problems addressed thus far were related to mass balance calculations; in
other words given values of some process variables (feed and product amounts or flow
rates, and component mole fractions), calculate values of other process variables.

Problems henceforth will also include some given thermodynamic properties or states
(such as temperature, pressure and phase) and you will be asked to calculate the heat
transferred to, or from the process system (one additional variable), which will require
writing and solving an energy balance equation (one additional equation).

Here is the procedure to follow for the energy balance:

• Perform all required material balance derivations (or calculations if appropriate)
as detailed previously
• Write the appropriate form of the energy balance (closed or open system) and
delete any of the terms that are zero/negligible for the given process system
• Choose a reference state-phase, temperature, and pressure-for each species
involved in the process. If enthalpy or internal energy for a species will be looked
up in a table (such as the steam tables for water), choose the reference state
used to generate the table; otherwise choose one of the inlet or outlet states as
the reference state for the species. Alternatively choose a path. 28
 Energy and Mass Balances
• Determine the inlet and/or outlet enthalpies (from tables if available, or from
equations) for each step of the path and calculate.
• The energy balance equation will usually be of the form ( assuming you can ignore
KE, PE and Work!):

∆𝐻 = 𝑛𝑖 𝐻𝑖 − 𝑛𝑖 𝐻𝑖 or ∆𝐻 = 𝑚𝑖 𝐻𝑖 − 𝑚𝑖 𝐻𝑖
𝑜𝑢𝑡 𝑖𝑛 𝑜𝑢𝑡 𝑖𝑛

𝑄= 𝑛𝑖 𝐻𝑖 − 𝑛𝑖 𝐻𝑖 or 𝑄= 𝑚𝑖 𝐻𝑖 − 𝑚𝑖 𝐻𝑖
𝑜𝑢𝑡 𝑖𝑛 𝑜𝑢𝑡 𝑖𝑛

29
 Reference States
For a reference state you need to specify a:
Temperature
Pressure
Phase

Specific Enthalpies of
Selected Gases (ideal)

30
Reference States

31
 Energy and Mass Balances
Example
300 L/h of a 20 mole% propane, C3H8 and 80% n-butane (C4H10) gas mixture at 0°C and
1.1 atm and 200 L/h of a 40 mole% C3H8, 60% n-C4H10 mixture at 25°C and 1.1 atm are
mixed and heated to 227°C at constant pressure. Calculate the heat requirement in
kJ/h. Enthalpies of propane and n-butane are listed below. Assume ideal gas behavior.

32
 Example
Energy and Mass Balances
Perform a mass balance. However, volumetric flowrate is given, therefore, the mass/molar flow
rate needs to be calculated. How?

Perform a mass balance. However, volumetric flowrate is given, therefore, the mass/molar flow
rate needs to be calculated. How?
For an ideal gas at an arbitrary temperature T and pressure P: PV =nRT
and for the same ideal gas at a specified reference temperature Ts and pressure Ps (referred to as
standard temperature and pressure, or STP:

The first equation divided by the second yields

33
Example
Energy and Mass Balances

34
 Energy and Mass Balances
Example

35
 Energy and Mass Balances
Example
Benzene vapor at 580°C is cooled and converted to a liquid at 25°C in a continuous
condenser. The condensate is drained into 1.75 m3 drums, each of which takes 2.0
minutes to fill. Calculate the rate (kW) at which heat is transferred from the benzene
in the condenser. The following information is given.

36
 Energy and Mass Balances
Example
Perform a mass balance (trivial in this case, as in=out).
However, volumetric flowrate is given, therefore, the mass/molar flow rate needs to
be calculated. How?

Choose a path to represent the enthalpy changes

= -18,986 kW 37
Example Energy and Mass Balances
The figure below shows a hot gas stream at 500°C being cooled to 300°C by
transferring heat to the liquid water that enters at 20°C and exits at 213°C. Assume
that the heat exchanger is insulated. The cooling water does not mix with the gas.
Calculate the flow rate of the cooling water.
.

(213oC)

Compound Cp Equation (Cp is in J/mol oC)

Nitrogen (g) 31.15 − 0.01357𝑇 + 2.68 ∗ 10−5 𝑇 2 − 1.168 ∗ 10−8 𝑇 3
Methane (g) 19.25 + 0.05213𝑇 + 1.197 ∗ 10−5 𝑇 2 − 1.132 ∗ 10−8 𝑇 3
Carbon Dioxide (g) 19.80 + 0.07344𝑇 − 5.602 ∗ 10−5 𝑇 2 + 1.715 ∗ 10−8 𝑇 3
Water (g) 32.24 + 0.001924𝑇 + 1.055 ∗ 10−5 𝑇 2 − 3.596 ∗ 10−9 𝑇 3
38
Water (l) 72.43 + 0.0104𝑇
Example
Energy and Mass Balances

𝑄= 𝑛𝑖 𝐻𝑖 − 𝑛𝑖 𝐻𝑖 = 𝟎
𝑜𝑢𝑡 𝑖𝑛

39
Example
Energy and Mass Balances

(213oC)

Compound Cp Equation (Cp is in J/mol oC)

Nitrogen (g) 31.15 − 0.01357𝑇 + 2.68 ∗ 10−5 𝑇 2 − 1.168 ∗ 10−8 𝑇 3
Methane (g) 19.25 + 0.05213𝑇 + 1.197 ∗ 10−5 𝑇 2 − 1.132 ∗ 10−8 𝑇 3
Carbon Dioxide (g) 19.80 + 0.07344𝑇 − 5.602 ∗ 10−5 𝑇 2 + 1.715 ∗ 10−8 𝑇 3
Water (g) 32.24 + 0.001924𝑇 + 1.055 ∗ 10−5 𝑇 2 − 3.596 ∗ 10−9 𝑇 3
Water (l) 72.43 + 0.0104𝑇

40
Example
Energy and Mass Balances

(213oC)

41
 Non-ideal Mixing
When ideal gases are mixed; is there any change in enthalpy; is there a release of
energy or is energy needed to effect the mixing?
No, there is no heat of mixing.
What about liquids; when two liquids are mixed is there a release of energy or is
energy needed to effect the mixing?
It depends!
When two “Ideal” liquids are mixed, the “heat of mixing is zero; for example ethanol
and methanol.
What about water and sulfuric acid?
NEVER ADD WATER TO ACID
Heat is released (exothermic process); the resulting mixture has a lower energy level
than the original two compounds and the heat of mixing is negative:

(𝑻)
∆𝑯𝒎𝒊𝒙 = 𝑯𝒎𝒊𝒙𝒆𝒅 − 𝑯𝒖𝒎𝒎𝒊𝒙𝒆𝒅
However, in general most liquids do not mix together (e.g. lemon/vinegar/oil) and thus
in order to effect mixing, energy needs to supplied (endothermic process)

42
 Standard Heat of Formation
Standard heats of formation is the name given to the special enthalpy
change associated with the formation of 1 mol of a compound from its
constituent elements (and products) in their standard state recorded at
the standard reference temperature and pressure. This is represented
by: 𝒐
∆𝑯𝒇

A standard state is a particular state of a species at temperature T and at

specified conditions of pressure, composition, and physical condition as,
e.g., gas, liquid, or solid.

The standard temperature and pressure are 1 bar (some state 1 atm)
and 25o C; the standard states used are states of the pure species are:
Gases: The pure substance in the ideal-gas state at 1 bar and 25o C.
Liquids and solids: The real pure liquid or solid at 1 bar and 25oC.
43
 Standard Heat of Formation
What is the standard heat of formation of elements and diatomic gases?
That is at 25oC and 1 bar what is the standard heat of formation of
Carbon (s), H2 (g), Br2 (liq)? 𝒐
∆𝑯𝒇 = 0
Therefore how do we determine the standard heat of formation of say
CH4. Note that the standard heat of formation of CH4 is given by the
following reaction:
C (s) + 2 H2 (g) → CH4 (g)

This cannot be usually determined in the lab!

Note that:
∆𝑯𝒐𝒇 = 𝑯𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − 𝑯𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
= 𝑯𝑪𝑯𝟒 − 𝑯𝑪 + 𝟐𝑯𝑯𝟐
= 𝑯𝑪𝑯𝟒
44
Standard Heat of Formation in J/mol

45
Standard Heat of Formation

46
 Standard Heat (Enthalpy) of Reaction
Chemical reactions are accompanied either by the transfer of heat or by temperature
changes during the course of reaction-in some cases by both. These effects are
manifestations of the differences in molecular structure, and therefore in energy, of
the products and reactants.
For example, the reactants in a combustion reaction possess greater energy than do
the products, and this energy must either be transferred to the surroundings as heat
or produce products at an elevated temperature.
Consider the reaction:

The standard heat of reaction is defined as the enthalpy change when a moles of A and
b moles of B in their standard states at temperature T react to form l moles of L and m
moles of M in their standard states at the same temperature T.

∆𝑯𝑶
𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 = 𝑯𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − 𝑯𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
= 𝝂𝒊 𝑯𝒊

= 𝝂𝒊 𝑯𝒊 − 𝝂𝒊 𝑯𝒊
𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
47
 Determination of heats of reaction from standard heat of formation

So let us return to the standard heat of formation of CH4. Note that the standard heat
of formation of CH4 is given by the following reaction:

C (s) + 2 H2 (g) → CH4 (g)

Given that ∆𝑯𝒐𝒇 = 0 for C(s) and H2, how do we proceed?

We need to find a path that will allow us to utilize existing data from other reaction(s)
(e.g. experiments) to arrive at an answer.

We use Hess’s Law.

A+B → C ∆𝑯𝑶
𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏𝟏

C+B → E ∆𝑯𝑶
𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏𝟐

A + 2B → E ∆𝑯𝑶 𝑶 𝑶
𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 = ∆𝑯𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏𝟏 + ∆𝑯𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏𝟐
48
Determination of heats of reaction from standard heat of formation
Example: determine the heat of formation of CO ; i.e.
C + ½ O2 → CO ∆𝑯𝑶𝒇 =?
From the following reactions using Hess’s Law

C + O2 → CO2 ∆𝑯𝑶
𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 = −𝟑𝟗𝟒 𝒌𝑱/𝒎𝒐𝒍 (1)

CO + ½ O2 → CO2 ∆𝑯𝑶
𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 = −𝟐𝟖𝟑 𝒌𝑱/𝒎𝒐𝒍 (2)

CO2 → ½ O2+ CO ∆𝑯𝑶

𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 = 𝟐𝟖𝟑 𝒌𝑱/𝒎𝒐𝒍 (2*)

(1) + (2*) leads to C + ½ O2 → CO ∆𝑯𝑶

𝒇 = −𝟑𝟗𝟒 + 𝟐𝟖𝟑 = −𝟏𝟏𝟏 𝒌𝑱/𝒎𝒐𝒍

49
 Determination of heats of reaction from standard heat of formation
When chemical equations are combined by addition, the standard heats of formation
may also be added to give the standard heat of the resulting reaction. This is possible
because enthalpy is a property, and changes in it are independent of path.

Consider the reaction:

This is the reverse water-gas shift reaction takes place only at temperatures well above
298.15 K (25°C). However, the data used are for 298.15 K, and the initial step in any
calculation of heat effects concerned with this reaction is to evaluate the standard
heat of reaction at 298.15 K. The pertinent formation reactions and heats of formation
are:

Since the reaction is carried out entirely in the gas phase at high temperature,
convenience dictates that the standard states of all products and reactants at 25°C be
taken as the ideal-gas state at 1 bar, even though water cannot actually exist as a gas
at these conditions. What is the standard heat of reaction? 41 166 J
50
Determination of heats of reaction from standard heat of formation
∆𝑯𝑶
𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 = 𝑯𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − 𝑯𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
= 𝝂𝒊 𝑯𝒊

= 𝝂𝒊 𝑯𝒊 − 𝝂𝒊 𝑯𝒊
𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔

51
Determination of heats of reaction from standard heat of Combustion
So let us return to CH4. From the information given below, calculate the standard heat
of formation of methane gas.

C(s) + O2 (g) → CO2 (g) ∆𝑯𝑶

𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 = −𝟑𝟗𝟒. 𝟎 𝒌𝑱/𝒎𝒐𝒍 (1)

H2 + ½ O2 → H2O (l) ∆𝑯𝑶

𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 = −𝟐𝟖𝟓. 𝟖𝟒 𝒌𝑱/𝒎𝒐𝒍 (2)

CH4 + 2O2 → 2H2O (l) + CO2 (g) ∆𝑯𝑶

𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 = −𝟖𝟗𝟎. 𝟑𝟔 𝒌𝑱/𝒎𝒐𝒍 (3)

C (s) + 2 H2 (g) → CH4 (g) ∆𝑯𝒐𝒇 = ?

(1) + 2*(2) – (3) leads to ∆𝑯𝒐𝒇 = −𝟑𝟗𝟒 − 𝟐 ∗ 𝟐𝟖𝟓. 𝟖𝟒 − −𝟖𝟗𝟎. 𝟑𝟔 = −𝟕𝟓. 𝟑𝟐 𝒌𝑱/𝒎𝒐𝒍

52
Determination of heats of reaction for incomplete reactions

53
Determination of heats of reaction for non-standard conditions

54
Example

55
 Example
The reference temperature is 25°C. The outcome of the material balance and some
needed enthalpy data are as follows:

56
 Example
The reference temperature is 25°C. The outcome of the material balance and some
needed enthalpy data are as follows:

57
Example

58