CHEMICAL ENERGETICS

KEY CONCEPTS

1. System 3. Properties of system

Intensive properties
Open System
 Those properties whose values, on
Exchange of matter and

Properties of system
division of system, remain same in any
energy both occurs with
part of the system are called intensive
surroundings
properties.
(Part of the universe under
study is system)
System

Closed System Extensive properties

Exchange of energy but  Those properties whose values in any part
not matter occurs with of the divided system are different from
surroundings the values of the entire system are called
extensive properties.

Ex : -
I II
Isolated System III IV
Neither matter nor energy is
This container is filled with an ideal gas at a
exchanged with surrounding definite T.
 Intensive properties : Pressure, temperature,
concentration, density, refractive index,
2. Surrounding viscocity, surface tension, molar volume,
dipole moment gas constant, specific heat
capacity, vapour pressure, specific gravity,
Part of universe excluding system is surroundings.
dielectric constant, EMF of a dry cell etc.
 Extensive properties : Volume, energy, heat
capacity, enthalpy, entropy, free energy, length,
mass etc.

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4. Process 5. Internal energy (U or E)

 E = Et + Ev + Er + Ee + En + Ep etc.
Isothermal
 T = 0  Absolute value of E can not be determined.
 U = 0(for ideal gas)
 H = 0(for ideal gas)
 E can be found for a process
Isobaric
 E  T (for ideal gas)
 P = 0
 H = QP
 E = nCVT (Here CV = molar heat capacity at
Isochoric constant volume)

 V = 0
 WP-V = 0 6. Reversible (or quasi-static) and
 U = QV Irreversible process

Adiabatic
(i) If a process is carried out in such a way that at
Q=0 every moment the system departs only
infinitesimally from an equilibrium state the
Cyclic process is called a quasi-static process.

 U = 0
Process

(ii) At each state system remains virtually in a state

 H = 0 of equilibrium. (In quasi-static process)
 S = 0
(iii) Any process which is not reversible is
P A B irreversible.
D C

V
(cyclic process
on P-V graph)

Free expansion
 Pext = 0
Q=0
 WP-V = 0
 U = 0
(for ideal gas)

Polytropic
 PVa = constant
 a = polytropic index
 If a =  then process is
adiabatic
 P-V work in various processes
(for ideal gas) w = –  PdV (P = External pressure)

Isothermal
process
7. P-V work in various processes

Free Polytropic Cyclic

expansion process process
Rev. Irrev. W=0  W = area of cyclic
P V P V
W = – nRT n V2/V1 W 2 2 1 1
W = – Pext (V2–V1) a 1 curve on PV-diagram
= – nRT n P1/P2 = – nRT (1 – P2/P1) Isobaric Adiabatic
process process
= – PV n V2/V1 = – nRT (1 – V1/V2)  Wcyc. = W for all
W = – Pext (V2 – V1) W = nCVT
= – PV n P1/P2 step in process
= – nR(T2 – T1)  nR 
  T
  1 
 If process is in
 P V P V 
  2 2 1 1  clockwise direction
  1 
(on PV-diagram) then
Isochoric
process work done is "–"
other wise "+"
W=0
  If Q heat is given to system and W work is
8. Sign convention for work and heat done on system then change in internal energy
of system E, can be given as
According IUPAC convention : -
E = Q + W
 Work done by system  –ve sign
 Work done on system  +ve sign 12. Enthalpy or Heat content (H)
 Heat absorbed by system +ve sign (i) H = U + PV
 Heat given by system  –ve sign
(ii) H = U + (PV)
9. Heat (Q)
(i) Heat is defined as the energy that flow into or Free
out of a system because of a difference in expansion
temperature between system and surrounding.
 H = 0
(ii) Q = m × S × T …(1)
Here m = Mass of substance in system Isothermal
Process
S = Specific heat
 H = 0
T = Change in temperature of system
Q = m × S × T Isobaric
Process
m
 Q= × (M × S) × T (for ideal gas)  H = U + PV = QP
M
   (M = molar mass)
Enthalpy change

Isochoric
 Q = n × C × T …(2) Process
m  H = U + VP
   (n = no. of moles = and
M
C = molar heat capacity ) Adiabatic
Process
(iii) At constant volume
 H = nCPT
(iii)

QV = n CVT …(3)  nR 

  T
(iv) At constant pressure   1
QP = nCPT …(4) = W

10. Zeroth Law of thermodynamics Cyclic

Process
Two systems in thermal equilibrium with third  H = 0
system are also in thermal equilibrium with each
other.
Polytropic
Process
11. First law of thermodynamics
 H = nCPT
 H = U + (a – 1)W
 Total energy of a system and its surrounding
must remain constant, although it may change
from one form to another.
(iv) If enthalpy of a closed system is taken as a function Notes : (1) T2'  T2
of temperature and pressure, then
(2) T2' can be found by following relation
 H   H 
dH    dT    dP 1  1  P 
 T P  P T T2'  T1   1   2 
     P1 
At constant pressure :
 H  14. Thermochemistry
dH    dT (because dP = 0)
 T P (A) Enthalpy of a substance
 H   Each substance has fixed quantity of enthalpy.
 dq P    dT (dH = dq P )
 T  P
 For one mole of a substance the enthalpy is
dq  H  represented as Hm.
 CP  P   
dT  T P (B) Standard state of a substance
(v) Relationship between H and U (for ideal  For a pure solid or pure liquid standard state is
gas) defined as the state with P = 1 bar and
temperature T (Specified temperature).
(a) H = U + (PV)
 H = U + nRT  For a pure gas, the standard state at temperature
T is chosen as the state where P = 1 bar and the
(If gas is not undergoing any chemical change) gas behaves as an ideal gas.
(b) For a chemical reaction  The symbol for a standard state is a degree
H = U + (PV) subscript (read as "naught", "zero" or
"standard"), with the temperature written as a
 H = U + (ng)RT subscript.

13. Adiabatic process (C) Enthalpy of reaction

(i) Definition of Enthalpy of Reaction : Enthalpy
Rev. Process of reaction is the enthalpy change for the unit
 W = C v,m (T2 – T1) extent of reaction. It is represented by the symbol,
H
 T2 < T 1 rH. Thus rH =
(Expansion)


 U = n C v,m (T2 – T1)
Adiabatic process

 H = n C p ,m (T2 – T1) Here  = extent of reaction


 PV = constant (ii) Unit of Enthalpy or Reaction :
 TV – 1 = constant
T unit of H kJ
  1 = constant unit of rH =   kJ moL1
P unit of  mol

(iii) Enthalpy of reaction refers to the entire

Irrev. Process chemical equation and not to any particular
reactant or product.
 W' = nCv, m (T'2 – T1)
 T'2 < T1 (iv) Expression of Enthalpy of Reaction : The
 U' < nCv, m (T'2 – T1) enthalpy of a reaction may be computed using
 H' < nCp, m (T'2 – T1) the expression
 PV  constant
rH  
products
 BH m (B)  | 
reactants
B | H m (B)
 (v) Exothermic and Endothermic nature of a
reaction : Since
– | 
reactant
B | fHº (B)

rH  
products
 BH m (B)  | 
reactants
B | H m (B) (E) Hess's Law of constant heat summation
The heat absorbed or evolved in a given chemical
two cases may be distinguished. reaction is the same whether the process occurs in
(a) Exothermic reaction : In a case where the one step or several steps.
enthalpy of products is less than that of (F) Enthalpy of Combustion
reactants, we have
It is the enthalpy change when one mole of a
rH = negative
compound combines with the requisite amount of
(b) Endothermic reaction : In a case where oxygen to give products in their stable forms.
the enthalpy the of products is greater than
that of reactants, we have (G) Integral Enthalpy of solution : The integral
enthalpy of solution at the given concentration is
rH = positive the enthalpy change when one mole of the solute is
(D) Enthalpy of formation dissolved in a definite quantity of solvent to
produce a solution of a desired concentration.
(i) Definition : The standard enthalpy of
formation of the compound is the change in the While recording integral enthalpies of solution it is
standard enthalpy when one mole of the a general practice to state the amount of the solvent
compound is formed starting from the requisite in which 1 mole of solute is dissolved. Thus
amounts of elements in their stable state of
aggregation. HCl(g) + 10 H2O(l)  HCl(10 H2O)
(ii) The standard enthalpy of formation of element rH1 = – 69.488 kJ mol–1
in its stable state of aggregation at one bar
pressure and at specified temperature is Similarly
assigned a zero value.
(i) HCl(g) + 25 H2O)(l)  HCl(25 H2O) ;
The specified temperature is usually taken as
25ºC. rH2 = – 72.266 kJ mol–1
A few examples are : (ii) HCl(g) + 40 H2O(l)  HCl(40 H2O) ;
fHº (O2, g) = 0 rH3 = – 73.023 kJ mol–1
fHº(C, graphite) = 0
(iii) HCl(g) + 200 H2O(l)  HCl(200 H2O) ;
fHº(C, diamond)  0
rH4 = – 74.203 kJ mol–1
fHº(Br2, ) = 0
(iv) HCl(g) + aq  HCl (aq) ; rH5 = – 75.145 kJ mol–1
fHº(S, rhombic) = 0
Where rH5 represents the limit of enthalpy change
fHº(S, monoclinic)  0 when 1 mole of hydrogen chloride gas is dissolved
in a very large quantity of water. The resultant
fHº(P , white) = 0 solution is known as an infinite diluted solution.
fHº(P, black)  0 (H) Integral Enthalpy of Dilution : The integral
enthalpy of dilution is the change in enthalpy when
(iii) Enthalpy of reaction from Enthalpies of
a solution containing 1 mole of solute is diluted
formation : from one concentration to another.
rHº =  B fHº (B) (I) Differential Enthalpy of Solution : It is the
product enthalpy change when 1 mole of solute is dissolved
in a very large volume of a solution of known
 concentration so that there occurs no appreciable
change in concentration of the solution.
(J) Differential Enthalpy of Dilution : It is enthalpy
change when 1 mole of solvent is added to a large
volume of the solution of known concentration so
that there occurs no appreciable change in the
concentration of the solution.
(K) Enthalpy of hydration : Enthalpy of hydration of a
given anhydrous or partially hydrated salt is the
enthalpy change when it combines with the
requisite amount of water to form a new hydrated
stable salt. For example, the hydration of anhydrous
cupric sulphate is represented by
CuSO4(s) + 5H2O(l)  CuSO4.5H2O(g)
(L) Enthalpy of Neutralization : Enthalpy of
neutralization is defined as the enthalpy change
when one mole of H+ in dilute solution combines
with one mole of OH– to give rise to undissociated
water i.e., H+(aq) + OH–(aq)  H2()
Hneut ~ – 55.84 kJ mol–1
(M) Enthalpy of Ionization : Whenever a weak acid
(or base) reacts with a strong base (or acid), the heat
released is less than 55.84 kJ mol–1. It is because of
the fact that these acids or bases are not completely
ionized in solution. Some of the heat is consumed
in ionizing these acids and bases. This heat is
known as enthalpy of ionization.
(N) Enthalpy of precipitation : Enthalpy of
precipitation is the enthalpy change when one mole
of a precipitate is formed. For example
BaCl2 (aq) + Na2SO4(aq)  BaSO4(s) + 2 NaCl(aq)
 rHº = – 24.27 kJ mol–1
(O) Enthalpy of Formation of Ions
We knwo that
H+(aq) + OH–(aq)  H2O(l) ;
rHº = – 55.84 kJ mol–1
For above reaction, we write
fHº = fHº (H2O, l) – {fHº (H+, aq)
+ fHº(OH–, aq)}
Hence at 25ºC, we get
fHº(H+, aq) + fHº(OH–, aq) = fHº(H2O, l) – rHº
= [– 285.83 – (– 55.84)] kJ mol–1]
= – 229.99 kJ mol–1
By convention, the standard enthalpy of formation
of H+(aq) is taken to be zero.
Thus, rHº (OH–, aq) = – 229.99 kJ mol–1
(P) Bond Enthalpies
(i) The bond enthalpy is the average of enthalpies
required to dissociate the said bond present in
different gaseous compounds into free atoms or
radicals in the gaseous state.
(ii) The term bond enthalpy may be distinguished
from the term bond dissociation enthalpy which
is defined as follows.
The bond dissociation enthalpy is the enthalpy
required to dissociate a given bond of some
specific compounds.
(Q) Enthalpy of Transition
Enthalpy of transition is the enthalpy change when
one mole of one allotropic form changes to another.
For example
C(graphite)  C(diamond) trsHº = 1.90 kJ mol–1
15. Variation of enthalpy of a reaction with
temperature (Kirchhoff's relation)
(i) Following equation is known as Kirchhoff's
relation.
rH =  ( C )dT  I
r P
Here I = constant of integration
(ii) If CP independent of temperature
In this case, we have
 r HT2   r HT1   r CP (T2  T1 )
16. Second law of thermodynamics
(i) The essence of first law is that all physical and
chemical process take place in such a manner
that the total energy of the universe remain
constant.
(ii) However, it is observed that all processes have
a natural direction, i.e. a direction in which they
take place spontaneously. First law fails to
answer this. Another feature of the spontaneous
processes is that they proceed only until an
equilibrium is achieved.
(iii) The direction of a spontaneous process and that
it eventually reaches equilibrium, can be
understood on the basis of entropy concept
 introduced through the second law of One can think entropy as a measure of the degree of
thermodynamics. randomness or disorder in a system. The greater the
P disorder, in a system, the higher is the entropy.
T2
(P1, V1) A
B (P2, V2) 18. Calculation of entropy change
q2 General expression
(P4, V4) D C T2 V
T1 S = nCV ln + nR ln 2
q1 (P3, V3) T1 V1
V
T2 P
AB - Isothermal reversible expansion = nC P ln  nR ln 1
T1 P2
V2
q2 = – WAB = nRT2 ln
V1 Reversible and irreversible isothermal expansion
and contraction of an ideal gas
BC- adiabatic reversible expansion
wBC = nCV (T1 – T2) V2 P
S = nR ln = nR ln 1
V1 P2
CD - Isothermal reversible compression
V  Isobaric heating or cooling :
q1 = – wCD = nRT1 ln  4 
 V3  T 
 S = nCP ln  2 
DA – adiabatic reversible compression  T1 
wDA = nCV (T2 – T1) Isochoric heating or cooling :
efficiency of engine :
T 
 w Total q1  q 2 T2  T1  S = nCV ln  2 
=    T1 
q2 q2 T2
Adiabatic process :
q1 q 2
 = 0 for rev. cycle
T1 T2 T2 V
S = nCV ln + nR ln 2
T1 V1
q rev
 T 
 dS  0
for irreversible process
Entropy (denoted by S) is a state function. S = 0 for reversible adiabatic compression and
q rev expansion.
S   T 19. Third law of thermodynamics
Statements of second law of thermodynamics
"At absolute zero, the entropy of a perfectly
(i) No cyclic engine is possible which take heat crystalline substance is taken as zero", which means
from one single source and in a cycle that at absolute zero every crystalline solid is in a
completely convert it into work without state of perfect order and its entropy should be zero.
producing any change in surrounding. By virtue of the third law, the absolute value of
(ii) In an irreversible process entropy of universe entropy (unlike absolute value of enthalpy) for any
increases but it remains constant in a reversible pure substance can be calculated at room
process temperature
Ssyt + Ssurr = 0 q rev

for rev. process ST – S0K =
Ssyt + Ssurr > 0 for irrev. process T
Since, S0K = 0
Ssyt + Ssurr  0 (In general)
T
q rev
17. Physical significance of entropy ST = 
0
T
 Absolute entropies of various substance have been At high temp, Non
tabulated and these value are used to calculate H spontaneous
entropy changes for the reactions by the formula ; when T > ,
S
Sr = PS (products) – RS (reactants) G = +ve
Variation of Sr with temperature and pressure:
T Variation of Gibb's function (G) with temperature
(Sr )T2  (Sr )T1  (C p ) r ln 2
T1 and pressure :
p1 G = H – TS
(Sr ) p2  (Sr ) p1  n g R ln
p2 = U + PV – TS

20. Gibbs free energy (G) and spontaneity dG = dU + PdV – TdS + VdP – SdT
dG = VdP – SdT
A new thermodynamic state function G, the Gibbs
free energy is defined as : • At constant temperature
G = H – TS  G 
at constant temperature and pressure dG = VdP or   V
 P T
G = H – T S
If (G)T, P < 0 process is irreversible • At constant pressure
(spontaneous)  G 
dG = – SdT or    S
(G)T, P = 0 process is reversible  T  P
(Equilibrium)
(G)T, P > 0 process is impossible Relationship between G and Wnon-PV
(non spontaneous) dU = q + WPV + Wnon-PV
The use of Gibbs free energy has the advantage that for reversible process at constant T and P
it refers to the system only (and not surrounding)
To summaries, the spontaneity of a chemical dU + PdV – TdS = Wnon-PV
reaction is decided by two factors taken together : H – TdS = Wnon-PV
(i) the enthalpy factor and
(ii) the entropy factor (Gsystem)T,P = Wnon-PV
The equation G = H–T S takes both the factors – (Gsystem)T,P = (Wnon-PV)system
into consideration. Non-PV work done by the system = decreases in
(Hr)T.P. (Sr)T.P. (Gr)T.P. Remarks gibbs free energy
– ve + ve Always – ve Reaction is
spontaneous Some facts to be remembered :
+ ve – ve Always + ve Reaction non (i) Gr = (Gf)product – (Gf)reactant
spontaneous
At low temp., (ii) Hr = (Hf)product – (Hf)reactant
H Non (iii)Sr = (Sf)product – (Sf)reactant
when T <
S spontaneous
G = + ve
+ ve + ve
At high temp.,
H
when T > Spontaneous
S
G = – ve
At low temp.,
H
– ve – ve when T < , Spontaneous
S
G = –ve
09.16 kJ