KNC1023: Engineering Physical Chemistry

Chapter 2: First Law of Thermodynamics

ASSOC. PROF. DR RUBIYAH BAINI

DEPARTMENT OF CHEMICAL ENGINEERING & ENERGY SUSTAINABILITY
Email: [email protected]
Tel: 082-583457
Work, heat and energy
Thermodynamics is the study of the
transformations of energy.
Work is the fundamental physical property in
thermodynamics.
Work is motion against an opposing force.
Example of work done,
 Expansion of gas pushes a piston or raising a
weight.
 Fuel burns in an engine produces mechanical
work
 Chemical reaction produces electricity
The energy of a system is its capacity to do
work.
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Work, heat and energy

Work is the motion against an opposing force.

Energy is the capacity to do the work.
Heat is the form of energy that causes difference in
temperature of two systems
Exothermic is a process that releases energy as heat into
its surrounding.
Endothermic is a process that energy is acquired from its
surrounding as heat.

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A steam engine is a heat engine that performs
mechanical work using steam as its working fluid. The steam
engine uses the force produced by steam pressure to push a piston
back and forth inside a cylinder. This pushing force is
transformed, by a connecting rod and flywheel, into rotational
force for work. 4
Basic Definitions
 System - volume of interest (reaction
vessel, test tube, biological cell, system surroundings
atmosphere, etc.) Energy
Matter
◦ Surroundings volume outside system
◦ Open system - matter can pass between Open System
system & surroundings
◦ Closed system - matter cannot pass between system surroundings
system & surroundings Energy
◦ Isolated system - Neither matter nor energy
can pass between system & surroundings
Closed System
 No mechanical or thermal contact

system surroundings

Isolated System

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Types of processes

Isothermal : the temperature of the system remains constant

Adiabatic : no heat can leave or enter the system
Isobaric: the pressure of the system remains constant
Isochoric: the volume of the system remains constant
Cyclic: the system returns to its original state after several
undergoing various changes
Reversible: a process in which the direction may be reversed at any
stage by a small change of variable like temperature, pressure, etc.
Irreversible: a process which is not reversible

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 The Internal Energy
 Total energy of a system (kinetic + potential) is called the internal energy (U)
 The change in energy from some initial state, i, to some final state, f, U is,

U = Uf – Ui

 Internal energy is a state function with its value depends only on the current state
of the system, path independent.
 Any change in state variable (e.g. pressure) results in a change in U
 Unit of energy (U, work, heat) is the joule (J) [kg m2 s-2]
 Internal energy is changed by either work (w) or heat (q) acting on system
 If work is done on the system (heat in), U increases
 If system does work (heat out), U decreases

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First Law of Thermodynamics

Mathematical summary of 1st Law:


U = q + w
Where,
q = heat transferred to a system,
w = work done on the system

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First Law of Thermodynamics
Expansion Work
 In differential form, the first law is:
dU = dq + dw
 Expansion work is the work by a change in
volume
◦ Consider a piston with change in volume, dV= Apistondz;
force is pexternal dw   p dV
ex

work total   w    p dV
V2

V1 ex

 -ve sign means the system moves an object against an

opposing force, pex

◦ Free expansion means the expansion against zero

opposing force, when pex = 0, then w = 0
◦ Expansion against constant pressure, pex = constant P Area = pex V
(e.g. atmosphere), w = - pex V (as shown in figure)

V1
V V2
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Reversible Change
• A reversible change in thermodynamics is a change that can be reversed
by infinitesimal modification of a variable.
• Example of reversibility is the thermal equilibrium of two systems
with the same temperature

• Reversible expansions
• pex = p along the path of the expansion.
• Thus, V2
dw  pdV and w    pdV V1

• If we know how p varies with V we can evaluate integral

• For ideal gas, p =nRT/V

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Isothermal Reversible Change
 In an isothermal reversible expansion, V2
temperature does not change w   pdV
◦ T is not a function of V and can be V1
removed from the integral V2 nRT
◦ For ideal gas, w = -nRT ln (Vf/Vi) w   dV
 If final volume > initial V1 V
(expansion), w < 0
V2 1
 System has done work on
surroundings internal w   nRT  dV
V1 V
energy(U) decreased
 If final volume < initial Vf
(compression), w > 0 w   nRT ln(V ) Vi
 System has work done on it, U
increased Vf 
 Note that as T increases |w| w   nRT ln 
increases  Vi 

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Reversible vs. Irreversible Change
• Irreversible expansion:
w= -pexV
• Reversible (isothermal)
P=nRT/V
expansion:
w=-nRTln{Vf/Vi}

• Which is greater? Reversible Work

A = RTln[Vf/Vi]
• Consider indicator diagram
• Work(rev.) = Area under curve
• Work (irrev.) = Area under rectangle Pex
• Work (rev.) > W (irrev.)
Irreversible work
A=p V

Vinitial Vfinal
Volume (V) 12
Heat Changes - Calorimetry

 Recall: dU = dq + dw
 If expansion work is dwexp and dwother is other work done (electrical,
magnetic, etc.), then dw = dwexp + dwother
 dU = dq + dwexp + dwother
 If V is constant, dwexp is zero since no PV work can be done
 Assume dwother is also zero, then dU = dq = qv
 qv is the change in q at constant volume
 Thus, measuring the heat change in a system at constant volume gives a
measure of the change in internal energy
 This process of measuring heat change is known as calorimetry
 One constant volume container for measuring heat change is a bomb calorimeter
 Demo on equipment
 In a bomb calorimeter, T  qv (means can find dU)
 This proportionality is quantified by calibration, typically by combusting a known substance

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Heat Changes - Heat Capacity
 If V constant, U increases as temperature
increases
 The rate of change of U at any temperature,
(U/T)V is called the heat capacity, CV
 This means that dU = qV= CV dT ≈ CV T
 You can estimate CV by determining the
amount of heat supplied to a sample
 Because qV ≈ CV T, for a given amount of
heat the larger CV, the smaller T

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Measuring Enthalpy Changes

Differential scanning calorimeter

 A device to detect the change in phase transition
 Thermogram: plot of Cp vs. temperature
 Peaks correspond to changes in enthalpy
 Area in the peak = H
 This technique is used in the chemical industry to characterize polymers in terms of
their stability when exposed to heat.

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Typical DSC
Thermogram

exothermic
Cp(dH/dt) mJ/s

Glass transition

melting
crystallization

endothermic

Temperature (K)
Source: www.chem.neu.edu/Courses/U331/CHM1222DSC.ppt

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Heat Changes - Enthalpy
 The enthalpy, H, is defined as
H= U + pV
◦ H is a state function
◦ At constant p, dH = dq (the change in enthalphy
= the energy supplied as heat at constant
pressure)
◦ Refer page 57 for the justification of dH = dq
◦ Cp is defined as dqp/dt = (H/T)p [refer to page 60]
◦ Refer to Table 2.2, page 60 for the value of constants.
 In most cases Cp > Cv
 For ideal gases, Cp = Cv +nR
 Cp – Cv = nR ~8 JK-1mol-1

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Variation of Cp with Temperature

 If Cp varies with temperature, you must integrate over the

temperature limits of interest.
 Approximate empirical expression C = a + bT +(c/T2)
p,m
 c 
dH  C dT  a  bT  
p
T 
2

H( T2 )
 T2
c 
 dH  a
   bT  
H (T 1)  T1 T  2

H( T2 )
b 1 1
 dH  a(T  T )  (T  T )  c(  )
2 2

H (T 1) 2 2 1
T T
2 1

2 1

 b 1 1 
H(T )  H(T )  a(T  T )  (T  T )  c(  ) 2 2
2

1
2 2
T T 
1 2 1

2 1

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Adiabatic expansion of an ideal gas
 To calculate the final state (Tf and Vf) assume a two
step process
 Step 1: Volume is changed and temperature held
constant
 Internal energy change = 0 since it’s independent of volume
the molecules occupy
 Step 2: Temperature changed from Ti to Tf
 Adiabatic so q = 0
 If Cv is independent of temperature, adiabatic work = wad=
CvT
 U = q + wad = 0 + CvT= CvT
 This says that for an adiabatic expansion the work done is
only proportional to the initial and final temperatures
 The relationship between initial and final volumes
can be derived using what we’ve learned about
reversible adiabatic expansions and perfect gases

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Adiabatic Expansion of an Ideal Gas
Relationship between T and V

 Given dq = 0 (adiabatic) and dw = -pdV (reversible expansion)

 dU = dq + dw =-pdV [1]
 For perfect gas dU = CvdT [2]
 Thus, combining [1] and [2], CvdT = -pdV [3]
 For an ideal gas, pV = nRT, so [3] becomes CvdT = -(nRT/V)dV [4]
or, rearranging, (Cv/T)dT = -(nR/V)dV [5]
 To obtain the relationship between Ti, Vi and Ti, Vi [5] must be integrated
 Ti corresponds to Vi
 Cv independent of T
 The adiabatic work, wad= CvT, can thus be calculated once this
relationship is found

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Integration of (Cv/T)dT = -(nR/V)dV
Tf 1 Vf 1
Cv  dT  nR  dV
Ti T Vi V

 Tf  V  V 
Cv ln   nR ln f   nR ln i 
V 
 Ti   Vi   f 
 Cv   T f   Vi 
  ln   ln 
 nR   Ti V 
  f 
 Cv 
  c
 Tf   nR   Tf   Vi 
ln   ln   ln , where c  Cv
V  nR
 Ti   Ti   f 
1
 Vi  c
or , T f  Ti  
V 
 f 

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Adiabatic Work, wad, and Temperature
wad  Cv T
wad  Cv T f  Ti  1
 Vi  c
But , T f  Ti   , where c  Cv
V  nR
 f 

  
1
c 
  Vi  
wad  Cv  Ti  Ti  C=3

  V f 
 
 
 
1
c 
  Vi  
wad  CvTi   1
  V f 
 
 
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pV Changes During Adiabatic Expansions
1 1

p i Vi Ti Tf Vi c Ti Vf c

for an ideal gas  but from adiabatic expansion    or   
p f Vf Tf Ti Vf  Tf Vi 
1

p i Vi Vf  c
1 nR • This relationship means that the product, pV
so,    where  doesn’t change as you go through an adiabatic
p f Vf Vi  c Cv expansion
• For ideal gas, the ratio of the heat capacities is
but we saw earlier nR is C p  C v so
>1 since Cp,m = Cv,m +R
nR C p  C v  C p = Cp,m /Cv,m = (Cv,m+R) /Cv,m
   1   1
Cv Cv Cv = 1 +(R /Cv,m)
• For monotomic gas, Cv,m= 3/2 R, so = 5/2
p i Vi Vf  p i Vf 
 1 
• For monotomic gas, Cv,m= 3 R, so = 4/3
Thus,    or   
p f Vf Vi  p f Vi 
rearranging,
p i Vi  p f Vf

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The First Law and Chemistry

 The study of heat produced from chemical reactions is called

thermochemistry
 We can apply what we learned from our 1st law considerations to the system
of reactants and products in a chemical reaction
 In a reaction, heat either flows into the system (endothermic reactions) or
out of the system (exothermic reactions)
 At constant pressure (reactions done in a beaker for example), the first law
tells us for
 Endothermic reactions H>0 {heat flows in}
 Exothermic reactions H<0 {heat flows out}
 Standard enthalpy change, Hø, is the change in enthalpy for substances
in their standard state
 Standard state is the form of the substance at 1bar (~1atm) and specified
temperature
 Hø298 is the standard enthalypy change at 1bar and 298K

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Enthalpies of Physical Change

 Changes in state (liquid to gas, solid to liquid, solid to gas, etc.) have
enthalpies associated with the transition, transHø
 Liquid-to-Gas, vaporization: vapHø
 Solid-to-Liquid, fusion: fusHø
 Solid-to-Gas, sublimation: subHø
 Table 2.4 gives symbols for a variety of transitions
 Because transition temperature is an important point, transition temperatures are often
listed at this point
 Recall that enthalpy is a state function. Thus, value is path independent.
 Can construct information if you don’t have it by making a path and summing the steps
 Example: You need the enthalpy of sublimation, but can’t find it
Path:
 Step 1 - solid to liquid (fusHø)
 Step 2 - liquid to gas (vapHø)
 Step 3 - sum of steps1 & 2
 Reverse of process involves only change of sign

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Enthalpies of Chemical Change
 The standard enthalpy of formation refers to the enthalpy typically at
1bar, and 298K .
 Enthalpies of reactions can be determined based on the following
equation,

 r H   v f H m   v f Hm
products reac tan ts
where v  stoichiometric coefficient of species
 For aA + bB  cC + dD,
rHøm = crHøm(C) + drHøm(D) - arHøm(A) – brHøm(B)
 The standard enthalpy of an overall reaction is the sum of the standard
enthalpies of the individual reactions into which it may be divided -
Hess’s Law
 Refer to page 51

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Temperature dependence of rHø
Kirkoff’s Law
 fHø is predicted to change with change in the temperature, and can
be estimated using the following equation:

T2
H (T2 )  H (T1 )   C p dT
T1
T2
 r H  (T2 )   r H  (T1 )    r C p dT
T1

where, r C p   vC p 
products

 p
vC 

reac tan ts

 This equation is known as Kirkoff’s Law

27
Exposure of the sun’s rays
causes human skin to generate
vitamin D, which is good for
bone health; increase the
brain's release of a good
hormone called serotonin.

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