3 Chemical Thermodynamics and Energetics

- - - - - - - - -- - - - - -, I1 Some lmoortant Formulae Iit --- - - - - -- - - - - - - - - - - .

V2
(2) wmox = - 2 .303 nRT log V
1
p (4) IJ = 1 kg m s-2 2
W = - 2 .30 3 nRT log 10 -
1
(3} max P2 lJ = 1 Pa m 3
lL atm = 101.3 J
(5) dU = dq + dW or ~u = q + w (7) AH 0 1:~H0 UH0
(6} H = U + PU (Reaction) (Reactant bonds) (Product bonds)
6.H = H2 - H 1
(8) AS
6.H = ~U + P~V
qp = 6.U + P~V (9) ASTotal = ~ssys + ASSUIT
6.H = qp (10) -G = H -TS (Gibbs energy)
6.H = 6.U + ruiRT -~G = AH - TAS
-AG = -TAS 101a1
- T = AH (~G = 0)
AS
- ~G = AG 0 + RT Zn Q
-~G0 = -RT Zn K or -2 .303 RT log 10 K
T
: (11} Oc = [Cf[D]: or QP = p~ x p~ (12) ~s = ST - S 0 or AS= fCpTdT
I [Ar[B] PA x PB
0
I (13} 6.S 0 = I.S 0 (products) - 1:S 0 (reactants)
POINTS TO REMEMBER (a brief concept )

Introduction

1• Definition: Thermodynamics is the branch of s cien ce t hat deals with different forms of energy, the quantitative
I
I
' . relationship between them and the energy changes that occur in physical and chemical processes.
Limitations:
(1) It concern with state of system and macroscopic properties.
,

(2) It does not deal with mechanism, rate and path of system and microscopic properties.

\FM Basic Concepts in Thermodynamics I

• System: A portion of the universe chosen to study the thermodynamic properties is called a system.
Sunoundings: All other parts of the universe outside the system where the observations are made are called
surroundings .
• Boundary: The surface separation between the system and the surrounding is called the boundary.

EM Types of System I
On the basis of exchange of matter and energy between system and surrounding, the system are classified as :
(1) Open system: can exchange both matte r and energy with its surroundings.
121 Closed system: can exc hange only en e rgy but not matter w ith the surroundings.
131 Isolated system: cannot exc hange e ithe r m a tter or e n ergy with its surroundings .

II__Properties of System I
(i)
Extensive property: Any prope rty of a system whose magnitude depends on the amount of matter present in
th e system is called its extensive property •
e.g. Mass, volume, internal energy, heat capacity etc .
(u
l Inten
. s ive property: Any property of a system w h ose magmtu
· d e is
· m. d ependent of the amount of matter present
in the system is called its intensive property .
e.g. M.P., B.P., Refractive index, etc.

(101)
I
I

102
Uttam 's MHT-CET (Chern IS/'
1

State and State function• \

• State function: lt is defined as any property of a system whose value depends on the current state of the
system and is independent on path followed to reach that state .
• Thermodynamic equilibrium: A system is said to be in thermodynamic equilibrium when the state functions 01
the system do not change with time.

•M Types of Proceuea
~

Isothermal Isobaric lsochoric Adiabatic Reversible =:J

(t.V = 0) (q = 0) . . inf
(t.U = 0) (t.P = 0) Dnvmg ) Opposite
(T = constant\ (P = constant) (V = constant) (No exchange of Heat) force force
(can be reverse)

Features of Reversible Proceu \

\ 1) The Driving and opposing forces are only infinitesimally different from each other.
\2) Process can be reverse
(3) Talces place in an infinite number of steps.
\4) Max. work obtained.
(5) Attain mechanical equation.
\6) Slow, T-P equation

'Mature of Heat and Work

Pressure - volume work, W = PV
Expreuion for preuure - volume work (P-conatant):
w = p ex ·l:!..V = - p ex (V 2 -v I l
Free expanaion: As pex = o, w = o
Concept of maximum work: Changes are reversible, in infinite numbe f . . ,
greater than opposite force and system in m h . al .. . r o steps, dnvmg force is infinitesimally'
ec an1c equ1bbnum
Expreuion for maximum work (P-Variable): · I
Wmax - 2 .303 nRT log lO v 2
V1
Wmax = - 2 .303 nRT log 10 .!J._
P2
Work and heat are path function. (.,

Unit of energy and work: The unit used to report energy is J 1 (J) 1
Sign conventiona of W and q: ou e L-atm = 101.3 J
+q = Heat a bsorbed by system from surrounding
-q = Heat is relea sed by system to surrounding
+W = Work is done on the system by surrounding
- W = work is done by the system on surrounding

Internal Energy (U)

It 's sum of kinetic energie s of all molecules , ions and atoms, the potential ene rgtes
• and all oth ki d f ·s
i.e. the grand total of energy of substance. er n o energie
~U = +ve = Work done on the system or heat supplied to system
~U = - ve = Work done by the system on surrounding or Heat is removed from the system.

First Law of Thermodynamic, I

• Statement•:
( 1) Total internal energy of an isolated system is constant.
can be converted from one form to another but it cannot be created or destro ed.
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Chemical Thermodynamics and Energetics

(3) Total quantity of energy of the universe is constant.

t
(4) Whenever a quantity of one kind disappear an exactly equivalent amount of energy of 0th er kind muS
appear.
(5) Total amount of energy of a system and surrounding must remain constant.
* Equation: l\U = q + W
* Modified etatement: The sum of mass and energy of an isolated system remain constant.
st
* Proceu: 1 law of thermodynamics for various process -
(1) Isothermal (2) Adiabatic (3) Jsochoric (4) Isobaric

[i==-~J [i==-~J (l\U "'qV) £\U=qp-p~V

- Second Law of Thermodynamic■ I

* Statement•:
(1) The spontaneous flow of heat is always unidirectional from higher temperature to lower temperature.
(2) Heat cannot be completely converted into an equivalent amount of work without producing permanent
change either in the system or its surroundings.
(3) No machine has yet been made that has an efficiency unity.

■fM Enthalpy (H)

• Deflllition: The enthalpy of system is defined as the sum of the internal energy of the system and the energy
that arises due to its pressure and volume.
H =U +PV
And, l\H = l\U + Pl\V
l\H = qP (·: qP = l\U + P~V)

■fM Relationship between ~H and ~U for Chemical Reaction•

aH =au+ RT~n
* Work done in chemical reaction= W = -RT~n
* Conclltiom under which ~U = aH:
'V

( 1) Reaction in closed vessel

~u = o ,~v
(2) For solid (in reaction) or liquid substances
= OJ
Enthalpies of Physical changes
t
Enthalpy of Phase Enthalpy of Atomic
transition or molecular changes
t t
t t t t t t
Enthalpy of Enthalpy of Enthalpy of Enthalpy of Enthalpy of Enthalpy of
fussion (~ H) vapourisation sublimation ionisation atomization solution
(~,HJ (L\.u H) (i\-11 H) (L\.to H) (~H)

Thermochemiatry
(I) Enthalpy of chemical reaction fHeat of reaction): It is the difference between the sum of the enthalpies of
Products and that of reactants with every substance in a definite physical state and in the amounts (moles)
• represented by the coefficients in the balanced equation.
For reaction aA + bB ~ cC + dD
aH = :EH prCJducta - :EH reacwnta
llH - (cHc + dH 0 ) - (aHA + bH 8 )
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Uttam 's MHT-CET (Chemistry)

For Exothermic reaction, 6.H 0 = -ve

It Endothermic reaction , 6.H 0 = +ve
* For Standard enthalpy of chemical reaction (!1H 0 )• It · h ·
. . . • IS t e enthalpy change accompanying the reaction when
all the substances mvolved a re 10 their standard states.
(2) Standard enthalpy of formation (!1,H 0 )· It · th ha!
• IS e ent PY change that accompanies a reaction in which one
th
mole of e pure compound in its standard state is formed from its elements also in their standard states.
For reaction aA + bB - ~ cC + dD
0 0
6.H [ct1rH (C) + d t1rH°(D)J - [at1rH0 (A) + b,\H 0 (B)]
0
= Li:1 H
f (produc t)
- ri:1 f H (rea
0
c ta nts )
0 0
* ilrH (C) = ilrH (H 2 ) = L1rH 0 (Cl2 ) = 0
0
(3) Enthalpy of combustion (!1cH ): It is the standard enthalpy change accompanying a reaction in which 1 mole of
the substance in the standard state reacts completely with oxygen or it completely burn.
(4) Bond enthalpy (Bond energy): The enthalpy change required to break a particular covalent bond in 1 mole of
gaseous molecul es to produce gaseous atoms and/or radicals is called bond enthalpy.
0
6.H = 16.H" (reactant bond) - It1H 0 (product bonds)
Hess's Law of Constant Heat Summation
* Statements: It states that the change in enthalpy for a reaction is the same whether the reaction takes place in

I
one or a series of steps.
OR
It can also be stated as the enthalpy change for a chemical reaction is the same regardless of the path by which
th e reaction occurs.
I* Applications: It can be used to calculate enthalpy of
'1t
Reaction Reaction Formation Combustion
(that is not possi ble to determine (that do not occur directly)
experimentally)

Spontaneous Process (Irreverssible Process)

process that takes place on its own without external expenses.
he natural (spontaneous) processes tend to occur in a direction that will lead to equilibrium.

Energy and spontaneity

* Energy is not only criterion for spontaneity of process .
* as t.H = +ve/-ve, it may be spontaneous or non-spontaneous

I
' *
,e Entropy I
It is thermodynamic property to measure molecular disorder
ordered state to disordered state = 6-S = +ve
di sord e red state to ordered state = LlS = - ve
I
I * Quantitative definition of entropy:
I ,:1S = q rev
T

Entropy and Spontaneity (2 nd Law of Thermodynamics)

/ * 2 nd Law of thermodynamics: The total entropy of the system a nd its s urroundings (universe) increases in a
s pontaneou s process .

II ,~ AS univer,e
L.l

AS
L.l lulal
= ,:1S.ro1a I = !1Ssvs1em + ,:\Ssurroundin g
> o ~
J

spontaneous
~:total < o ---7 non s pontaneo us
1
~ o tal =0 ---7 at equilibrium
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(_'l,e111ical T/1 ermo c~1·11w11ics und Fncrgetics

Gibbs Energy (G) ]

* G = H - TS whe re, H = enthalpy a nd S = entropy, T = tempe rature
* Chan ge in Gibb 's e ne rgy a t consta nt te mpe rature and pre ssure is given by
~G = ~ H - T t. S
- Gibb's Energy and Spontaneity J

* ~G = - Tt. Stntol
t.G < 0 ~ spontaneous
~G > 0 ~ nonsponta neous
f!G = 0 ~ at equilibrium

- ~G and Equilibrium constant

6G = ~G 0 + RT lnQ
At equilibrium , t.G = 0 and Q = K
~G 0 = - RT ln K = -2.303 RT log 10 K

EJI Third Law of Thermodynamics

* Statement: it states that the entropy of a perfectly ordered crystalline substance is zero at absolute zero of
temperature .
S = 0 at T = 0
o C -dT
~S = S T - S O = S T = f---'-P__
T
0

~S 0
= ( cs~ + dS~) - (as~ + bS~)
Standard Molar Entropy (S 0 )
* Definition: The absolute entropy of on e m ole of a pure substance at 1 atm pressure and 25°C is called standard
molar entropy of the substance.
* Usefulness of standard molar entropy:
(1) By knowing the values of standard molar entropy of all reactants and products in a chemical reaction. it is
possible to calculate ~S 0 for the reaction .
(2) It is useful to compare entropie s of different substances under the same conditions of temperature and
ressure.
000