CENG 1000: 

Introduction to Chemical and Biomolecular Engineering

Ying Chau| Fall 2016
Lecture 14: Energy balance and energy storage 
 By the end of the lecture, you should be able to:

‐ Apply energy balance to steady‐state processes that involve phase changes and 
chemical reactions
‐ Describe the process of  thermochemical energy storage 
‐ Apply the concept of “heat of reaction” to thermochemical energy storage
‐ Describe the criteria in material choice for thermochemical energy storage 
Energy balance summary
 From a physical standpoint, we can categorize energy into macroscopic kinetic energy 
( ), macroscopic potential energy ( ), and internal energy ( ).
 There are 3 ways energy can be transferred across system boundaries: heat ( ), work 
( ) and energy carried by molecules.
 Energy balance (First Law of Thermodynamics), ignoring KE and PE changes: 

Closed systems ∆
Steady‐state flow 
open systems
0
Heat transfer summary
 Conduction         


=  k is thermal conductivity [W/moC]


 Convection         

=  T  h is convective heat transfer coefficient [W/m2 oC]

Thermal energy storage summary
Sensible heat storage
Energy is stored as a result of temperature change

c T c is specific heat capacity

Latent heat storage

Energy is stored as a result of phase change at a constant
temperature, usually from solid to liquid phase

l l is latent heat (of fusion)

Solar Energy Storage System  

Adapted from O. Ercan Ataer, (2006), STORAGE OF THERMAL ENERGY, in Energy Storage Systems, [Ed. Yalcin Abdullah Gogus], in
Encyclopedia of Life Support Systems (EOLSS)
Example: sensible heat storage system (completed in last class) 
The average solar power transferred to heat exchanger (HX) 1 per unit area is 300W/m2 over 8 hours day 
time period. The area of this heat exchanger is 7 sq. m Water is circulated between the heat exchanger 
and the water tank of 350L in volume. 
 Q1: What is the mass flow rate through heat exchanger 1 if the water stream temperature increases by 
1oC in a single pass? 
 Q2: The initial temperature of water in the tank is 20oC (in the beginning of the day). What is the 
expected temperature rise at the end of a day? 
 Q3: At night time, temperature drops down to 10oC. Is the energy stored sufficient to warm a room of 
150 sq.ft over 10 hour? The average heater power required is 1500W. 
 Q4:  Heat transfer from heater to the room is by convective transfer. For the current heater 
configuration, h A = 75 W/K.  If the water tank volume is increased to 2000L, what problem may be 
anticipated? 
Homework problem
 Redesign the solar energy storage system to provide heating for a room size 
doubling in size
 1) How would you adjust the size of heat exchanger and the storage tank? 
 2) An engineer proposes replacing water with molten salt while keeping the storage 
tank size unchanged. Is it possible? Why or why not?  
Example: baby warmer for developing countries 
 Embrace® is a low‐cost device in lieu of baby incubator based on PCM

Wax-like
PCM
in a sleeping
bag
can keep the
baby warm
up to 6 hours
Example: baby warmer for developing countries 
Working with a partner to answer the following questions:

• Which paraffin would you choose as the PCM of the

baby warmer and why?

• For a normal baby, the resting metabolic rate at 40 W/m2

is able to produce enough heat to maintain the body
temperature. However, premature baby may suffer from
hypothermia (that is, body temperature is too low).
Assuming the body surface area of the newborn is 0.25
m2, what is the minimum amount of PCM required
for keeping the baby warm for 6 hours?

• What other product features do you consider to be

important and should be incorporated in the design?
Enthalpy changes with temperature and phase of material  

Cp

l (latent heat )

Cliquid
 Enthalpy of reaction 
Endothermic reaction  Exothermic reaction 
Enthalpy Enthalpy
Products Reactants

Hr = + Hr = -

Reactants Products

Reaction coordinate Reaction coordinate

Energy change due to reaction
 The enthalpy change that accompanies a reaction is called the heat (enthalpy) of 
reaction, ∆ . This results from the formation and breaking of bonds during the 
reaction.
 Breaking of bonds is endothermic, ∆ 0.
 Forming of bonds is exothermic, ∆ 0.
 In general, ∆ depends on the reaction and the conditions of the reactants and 
products. Usually they are available in tables at certain reference temperatures 
(typically 298 K). e.g.
1
H O →H O ∆ 286 kJ/mol (at 298 K)
2
 This means: at 298 K, if 1 mol of hydrogen gas and 0.5 mol of oxygen gas combines to form 1 mol
of liquid water, the heat of reaction is ‐286 kJ. Mathematically:
∆ 298K 298K 0.5 298K 286 kJ/mol
Example (heat of reaction)
 Consider the Haber process:

N 3H → 2NH ∆ 400 109 kJ/mol

Our reactor is maintained at 400 °C throughout. If the feed rates are 1 mol/s N2 and 3 mol/s H2, and 
NH3 is produced at 0.3 mol/s, calculate the cooling load (in kJ/s) needed to maintain the reactor at 400 
°C.
Thermochemical energy storage cycle
 Energy is stored in dissociation reaction and released in a 
reverse reaction. Energy is stored as chemical potential. 
(Compare this to the situation of sensible and latent heat storage)
 Types of reactions: 
 Sorption: involves the capture of gas vapor with a substance in 
condensed state (liquid or solid)
 Chemical reaction 
*Reactions are reversible 
* Reactants and products are in equilibrium 
 Three steps of thermochemical energy storage
 Charging: endothermic process for the dissociation from C to A and B. 
Enthalpy of reaction provided from an energy source (e.g. solar power)
 Storing: A and B are stored separately. Minimum energy loss, except 
cooling of component A and B and material degradation.
 Discharging: exothermic process  to recover the enthalpy of reaction

Abedin and Rosen, The Open Renewable Energy Journal, 2011

Advantages of thermochemical energy storage

 High energy storage density 
 More compact storage compared to sensible and latent heat storage
 Ambient storage 
 Low heat loss during storage
 Appropriate for long term storage
Materials for thermochemical energy storage (solid‐gas system) 

C(s) A (s) + B (g) Hr = +

Table: Steiger M. et.al. University of Hamburg

Graph: K. Edem N’Tsoukpoe, et.al. A review on long-term sorption solar energy storage, Renewable and Sustainable Energy Reviews, Volume 13, Issue 9, 2009, 2385–2396
Example: Energy storage by hydration/dehydration of 
magnesium sulphate
MgSO4 7 H2O (s) MgSO4 (s) + 7 H2O (g) Hr (120oC) =425 kJ/mol
Winter Summer
Question:
In summer time, hydrated magnesium sulphate
(MgSO4 7 H2O) enters at a molar flow
rate of and leaves the reactor completely
dehydrated. If heat is supplied at 1000 kW,
and assume the reactor at constant temperature
(120oC), calculate .

Schematic of the reactor in an open system:

reaction at atmospheric pressure and no gas storage
Figure: Kerskes H. et.al. Energy Procedia, 2012.
Example: Energy storage by hydration/dehydration of 
magnesium sulphate
Thinking point:
In actual operation, more heat is needed to maintain the same conversion rate. Why?

Thinking point:
In practice, less than 10% of the heat stored in dehydrated magnesium sulfate can be recovered in the
exothermic reaction. What may be hindering?

Figure: Steiger M. et.al. University of Hamburg

Materials for thermochemical energy storage (liquid‐gas system)

C A+B Hr = +
C <‐>  A + B  r (298K)  [kJ/mol] Charging temperature [K]
SO3↔SO2+1/2O2 98.2 1000 
NH4HSO4↔NH3+H2SO4 132 1013
CH4+H2O↔3H2+CO  206 1285
CH4+CO2↔3H2+2CO  247 1285
NH3↔3/2H2+1/2N2 66.5 751

Source: Dr Keith Lovegrove, Solar Thermal, IT Power Group

Ammonia based thermochemical energy storage 

charging
NH3(g) 3/2 H2(g) + 1/2 N2 (g) Hr (700K) = 46.2 kJ/mol
discharging
Charging and discharging: at 700K and 200 atm.
Storage: 298K and 200 atm. Ammonia is phase separated as liquid from hydrogen and nitrogen gas.
Dunn R. et.al. Proceedings of the IEEE, 2011.
Homework problem: 
Given the equilibrium curve and the charging conditions (700K,
200 atm), how much thermal energy can be stored for every
Equilibrium curves of dissociation of
mole of ammonia entering the reactor?
ammonia to hydrogen and nitrogen
Ammonia enters the reactor at 298K and 200 atm. Assume
reaction reaches equilibrium inside the reactor.
Hint: consider sensible heat, latent heat and
heat of reaction

Properties of reactants are given:

Boiling point of ammonia at (200 atm)= 438K
Latent heat of vaporization of ammonia (200 atm) =23331 J/mol

Cp (J/mol K)
NH3 (l) 81
NH3 (g) 42
H2 (g) 29
N2 (g) 30

Figure : Dunn R. et.al. Proceedings of the IEEE, 2011.

Criteria for choosing thermochemical energy storage materials
 Energy density  (How is this related to enthalpy of reaction?) 
 Reaction temperature (and pressure)
 Reaction rate 
 Reaction extent (related to Gibbs free energy, another thermodynamics 
concept)
 Cost and availability 
 Cycling behavior of materials (reversibility and degradation) 
 Safety: toxicity and corrosiveness
 Flow and heat transfer properties
Comparison of different types of thermochemical energy storage

Slide credit: Steiger M., et.al. University of Hamburg

Abedin and Rosen, The Open Renewable Energy Journal, 2011