Energy Balances

Fundamentals of Chemical Processes for Energy and Environment

Energy Engineering – Politecnico di Milano
Prof. Alessandro Donazzi
alessandro.donazzi@polimi.it
 Energy balances

The total energy of a chemical system, E is the sum of:

Internal Energy, U: energy associated with presence, relative position and motion of molecules, atoms and subatomic particles.

It mainly depends on temperature.

Kinetic Energy, Ek: energy associated with macroscopic motion of the system with respect to a fixed reference.

Potential Energy, Ep: energy associated with the overall mass and charge and the position with respect to external force fields

(gravitational, electro-magnetic).

E = U + Ek + Ep

Heat, Q is the energy transfer associated with temperature differences.

We state by convention: Q > 0 when entering into the system.

Work, W is the energy transfer associated with mechanical, electrical, etc.. forces. W > 0 when made on the system.

Energy unit: 1 Joule = 1/4.186 cal

 Energy balances

Mathematical implementation of the energy conservation law (1st law of thermodynamics). Considering a macroscopic control

volume:

Energy Accumulation = Energy input – Energy output

Two different cases can be considered: closed systems (without transfer of matter from system to surroundings) and open

systems (with transfer of matter from system to surroundings).

Closed systems:

ΔE = Q + W

Where ΔE is the total energy difference from the initial to the final state of the system. Compared with the large variations of

internal energy associated with chemical reactions, changes of kinetic and potential energies are typically negligible. Concerning

the transfer of work energy, two cases can be identified:

constant volume  W = 0 constant pressure  W = -Δ(PV)

 Energy balances

Accordingly, the energy balance equation can be rewritten as:

ΔU = Q at constant volume ΔH = Q at constant pressure

Where H = U + PV enthalpy (function of state).

Open systems: in this case, the flow-work 𝑃 𝑉̇ necessary to push against pressure a volumetric flow rate into and out from the

system must be considered. Assuming steady state conditions (no accumulation) in addition to the previous assumptions, the

energy balance, i.e. a power balance, can be written as:

Where Δ is the difference from inlet to outlet conditions. It is worth noting that energy quantities in this last equation are defined

per unit of time, and therefore units of power (e.g. W = J/s) must be used. Introducing enthalpy, we obtain:

Which is the classical form of energy balance for open systems, sometimes unproperly named as “thermal balance”.
 Energy balances

Evaluation of absolute values of both internal energy and enthalpy is not feasible, however in solving energy balances we are

interested in changes and not in absolute values. It is useful to consider changes with respect to one arbitrary reference state,

which is defined by temperature, pressure composition and physical state. We can write the balances as:

∆𝑈 = 𝑈 −𝑈 − 𝑈 −𝑈 =𝑄

∆𝐻 = 𝐻 −𝐻 − 𝐻 −𝐻 = 𝑄̇

Following a temperature change from Tref to T, the associated variations of molar internal energy and enthalpy are:

∆𝑈 = 𝐶 𝑑𝑇

∆𝐻 = 𝐶 𝑑𝑇

with CV and CP = molar specific heat at constant volume and pressure, respectively. For ideal gases the following correlation:

𝐶 =𝐶 +𝑅
In the equation, R is the universal gas constant.
 Energy balances

R value depends on units, as shown in the following Table:

8.314 m3 Pa/mol/K
0.08206 l atm/mol/k
1.987 cal/mol/k
8.314 J/mol/k

Specific heat values depend on temperature. Empirical T-functions are available in the literature for several gas species.

N2 CP/R = 3.280 + 0.593x10-3T – 0.040x105/T2 (298 < T < 2000 K)

O2 CP/R = 3.639 + 0.506x10-3T – 0.227x105/T2 (298 < T < 2000 K)

CO2 CP/R = 5.457 + 1.045x10-3T – 1.157x105/T2 (298 < T < 2000 K)

CO CP/R = 3.376 + 0.557x10-3T – 0.031x105/T2 (298 < T < 2500 K)

H2O CP/R = 3.470 + 1.450x10-3T + 0.121x105/T2 (298 < T < 2000 K)

Air CP/R = 3.355 + 0.575x10-3T – 0.016x105/T2 (298 < T < 2000 K)

T in K
 Heat of reaction, heat of combustion, heat of formation

Standard heat (enthalpy) of reaction, ΔH°R: enthalpy variation associated with the transformation under standard conditions ° of

a unit amount (usually one mole) of a reactant according to a given stoichiometry: α A + β B → γ C + δ D.

Standard conditions (reference state) are defined by temperature, pressure, composition and physical state. The choice is

arbitrary in principle, but a conventional definition is needed for practical reasons. i.e. to provide a common basis for data. For

example:

Composition: pure species.

Temperature: 25°C (298.15 K)

Pressure: 1 bar (new); 1 atm (old)

Physical state: the stable state at standard T and P, usually explicitly reported

Note that such definitions are very common but not universal. It is then necessary to check when using data. Also note that

standard conditions refer to ideal transformation not to real one, e.g. reactions require mixing of reactants and do not occur

between pure substances. Reactions with negative reaction heat are called exothermic. Reactions with positive reaction heat are

called endothermic.
 Heat of reaction, heat of combustion, heat of formation
Standard combustion heat (enthalpy), ΔH°C: standard enthalpy of combustion of a unit amount (mole, volume, mass) of a fuel

species. Note: the C, H, S e N content of the fuel is assumed to be oxidized to CO2 (g), H2O (l) o (g), SO2 (g), N2 (g), respectively.

Standard heat (enthalpy) of formation, ΔH°,F: standard heat of the formation reaction of a unit amount (usually 1 mole) of an i-th

species starting from the elements (species which contains only one atom type, e.g. C, O2, H2, S, N2).

C (graphite) + 2 H2 (g)  CH4 (g)

H2 (g) + 0.5 O2 (g)  H2O (g)

Hess’ Law (of constant heat summation): for any transformation (including a reaction) at constant P and T the enthalpy change

does not depend on the actual steps.

C (graphite) + O2 (g)  CO2 (g) H°1 = -393.8 kJ/mol

CO2 (g)  CO (g) + 0.5 O2 H°2 = +283.2 kJ/mol

C (graphite) + 0.5 O2(g)  CO(g) H°3 = H°1 + H°2 = -110.6 kJ/mol

 Other standard reaction enthalpies can be calculated from standard combustion enthalpies.
 Heat of reaction, heat of combustion, heat of formation

1) C (graphite) + 2 H2 (g)  CH4 (g) ΔH°1 = - 74.9 kJ/mol

2) H2 (g) + 0.5 O2 (g)  H2O (g) ΔH°2 = -242.0 kJ/mol

3) C (graphite) + O2  CO2 (g) ΔH°3 = -393.8 kJ/mol

4) CH4 (g) + 2 O2  CO2 (g) + 2 H2O (g) ΔH°4 = 2 ΔH°2 + ΔH°3 - ΔH°1 = -802.8 kJ/mol

 Standard reaction enthalpies can be calculated from standard formation enthalpies. This result has a general value since

stoichiometries are always consistent with the conservation law of atoms.

Heating value of a fuel: it is the heat released by combustion of a unit amount (1 mole, 1 kg or 1 Nm3) of fuel at constant

pressure and temperature. It is a positive quantity equal to the standard combustion enthalpy (negative) with sign changed.

Two heating values are defined depending on the assumption on the physical state of product H2O: Higher Heating Value (HHV)

if liquid, and Lower Heating Value (LHV) if vapor.

 Heat of reaction, heat of combustion, heat of formation
These two quantities are obviously related, their difference being equal to the latent heat of vaporization of the product water:

LHV = HHV - 25.0 (U + 9H) [kJ/kg]

Where U and H are the mass percentage of moisture and hydrogen in the fuel, respectively, and 2500 kJ/kg is the latent heat of

vaporization of water (at 0°C). HHV and LHV are equal in the case of H-free dry fuels. Since smoke temperature is usually higher

than dew temperature, LHV is the quantity that corresponds to the heat released. However in the absence of any specification the

reported values refer to HHV.

Heating value of solid fuels (coal) can be estimated starting from elemental composition (% w/w) with the Dulong formula:

HHV = 338.7 C + 1445 (H - O/8) + 94.3 S [kJ/kg]

 Heating values of some species

MM LHV HHV HHV LHV LHV

Fuel Formula
kg/kmol MJ/kg kcal/Nm3 kJ/mol kcal/Nm3 kJ/mol
Carbon C 12 32.8 4194 393.5
Hydrogen H2 2 121.0 3048 286 2579 242
Carbon monoxide CO 28 10.1 3016 283
Methane CH4 16 50.1 9486 890 8548 802
Ethane C2H6 30 47.6 16627 1560 15230 1429
Propane C3H8 44 46.4 23640 2218 21775 2043
Butane C4H10 58 45.8 30653 2876 28329 2658
Methanol CH3OH 32 21.1 8143 764 7205 676
Ethanol C2H5OH 46 27.8 15017 1409 13610 1277
Dimethyl ether C2H6O 46 28.9 15561 1460 14154 1328
Propanol C3H7OH 60 31.5 22030 2067 20165 1892
Acetylene C2H2 26 48.3 13845 1299 13387 1256
Benzene C6H6 78 39.6 34298 3218 32902 3087
Ammonia NH3 17 18.6 4071 382 3379 317
Hydrazine N2H4 32 18.1 7109 667 6171 579

Source: NIST Chemistry WebBook

 Adiabatic flame temperature
Adiabatic flame temperature: it is the theoretical maximum temperature achievable by the combustion of a given fuel air mixture.

It is calculated under the assumptions of total combustion under adiabatic conditions. Real combustion temperature will be usually

lower than the adiabatic one (e.g. due to incomplete combustion, heat losses, etc...). It is a useful input for combustor design

including the selection of construction materials.

Flame temperature for CH4 combustion:

adiabatic at stoichiometric conditions: 2010°C

with incomplete combustion: 1920°C

experimental: 1885°C

Calculation of adiabatic flame temperature (at constant pressure).

Let us consider the energy balance under adiabatic conditions. Starting from the balance on open systems, with Q = 0. We obtain:

It is convenient to assume the following refence state for calculation of enthalpies: inlet pressure and composition; temperature

equal to the one used for definition of standard combustion heat (usually 25°C).
 Adiabatic flame temperature
T Ad Tin
~ ~

products
ni   C P ,i dT  n f  H C0  
reac tan ts
ni   C P ,i dT  0
Tref Tref

H°C = standard combustion enthalpy at 25°C

nf = moles of burned fuel

ni = moles of i-species in feed (reactants) and outlet (products) stream

TIN = inlet temperature

TAD = outlet temperature, i.e. adiabatic flame temperature

The adiabatic flame temperature equation states that all the enthalpy release from combustion (plus the enthalpy which enters

the system with the feed stream) is available to increase the temperature of the products. This statement is more evident when

introducing the heating value (LHV) instead of the combustion enthalpy.

T Ad Tin
~ ~

products
ni   C P ,i dT  n f  LHV f  
reac tan ts
ni   C P ,i dT
Tref Tref

This latter formulation is particularly useful for complex fuel (e.g. coal), since calorific values are always available. In such cases

nf is usually the mass (kg) of burned fuel.

 Adiabatic flame temperature

An alternative approach consists of writing the inlet and the outlet enthalpy fluxes as the weighted sums of molar enthalpies of

the species, hi. The specific molar enthalpies of the i-th species are calculated assuming the following reference state:

standard temperature and pressure (usually 298.15 K and 1 bar), elementary species in the required amount for the i-species

formation. The following expressions can be derived:

,
,

hi = specific molar enthalpy of the i-th species at temperature T and in the physical state specified in the problem

Hf0F = formation enthalpy of the i-th species at the reference state

Note that this choice respects the rule of keeping the same reference state for both the inlet and the outlet streams. Indeed

irrespectively of the complexity of the reaction network the atomic balances must be closed. Accordingly the same amount of

elements is required to form both reactants and products.

 Adiabatic flame temperature

Adiabatic flame temperature: it is the maximum temperature theoretically achievable during the

combustion of a fuel/oxidant mixture. The adiabatic flame temperature assumes that the system is

adiabatic and the combustion is complete. It is a limit temperature: the real temperature is typically smaller,

due to unavoidable heat dissipation and inefficiencies in the chemical process. It allows for choosing

materials, calculating the size of combustion equipment and establishing the operative conditions (air

excess, inlet temperature).

Adiabatic flame temperature for C3H8 combustion:

Stoichiometric conditions (4.03% C3H8) 2067°C

100% air excess, lean mixture 1208°C

Stoichiometric pure oxygen O2 instead of air ~ 6300°C

9.4% C3H8, rich mixture 1710°C

Adiabatic flame temperature for propane/air mixtures