Heat and thermodynamics:

Temperature:
Temperature is often used to represent how hot or cold an object is? It is average K.E of
molecules, but to understand the temperature best we must understand the thermal equilibrium.

Thermal Equilibrium:
If two objects are at same temperature they are in thermal equilibrium.

Zeroth law of thermodynamics:

If two objects A and B are in thermal equilibrium with third object C then A , B are in
equilibrium with each other.
Temperature scales:

Fahrenheit scale

Ice point of water = 0 0C,

Steam point of water = 100 0C

Fahrenheit scale:
= 32 𝟎F

= 212 𝟎F

Kelvin scale:

= 273 K

= 373 K

Conversions:
Change in temperature:

Remember:
 Change in temperature is equal in Celsius and Kelvin scales.
 In Kelvin, temperature is measured in Kelvin only not in degree Kelvin.

Expansion OF Solids And Liquids:

Linear Expansion:

∆𝐿 = 𝛼 𝐿𝑖 ∆𝑇 (𝛼 = 𝑐𝑜𝑐𝑒𝑓𝑓𝑖𝑐𝑒𝑛𝑡 of 𝑙𝑖𝑛𝑒𝑎𝑟 𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑜𝑛)

Volume Expansion:

∆𝑣 = 𝛽𝑣𝑖 ∆ 𝑇 (𝛽 = 𝑐𝑜𝑓𝑒𝑐𝑖𝑒𝑛𝑡 𝑜𝑓 𝑣𝑜𝑙𝑢𝑚𝑒 𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑜𝑛)

𝛽 = 3𝛼 (PPSC 2015)
Water Expansion:
As temperature increases from 0 0C 𝑡𝑜 4 0C, water contract and density increase.

Above 40C Water expand and density decreases.

Maximum density of water is at 40C (39.16 F)

Ideal Gas:
Any low density gas is referred to ideal gas.

Equation of State:
PV= nRT (no. of moles)
PV= 𝑁𝑘 𝑏 (no. of molecules)
Where 𝑘𝑏 is Boltzmann constant having value 1.38× 10−23 𝐽/𝐾
Remember:
 P,V,T are known as a thermodynamics variables

 Holes on heating expand in size.

 Kelvin scales not contain degree sign due to absolute value.

 Volume is an extensive variable. (Extensive Variables are those variables which

depends on size of the system)
 Temperature ,pressure ,density are intensive variables. (Does not depend on size of
system)

 P,V,T are the microscopic properties of the system.

 Pendulum clock Becomes slower in summer and faster in winter.

Internal Energy:

Sum of all energies of the system.

Heat: Transfer the energy across the boundaries of system or agitation of atoms or molecules.

Unit: Calories, joule (SI Unit), Btu

Mechanical equivalent: 1Cal = 4.186 J

Heat Capacity: Amount of energy needed to raise the temperature of sample by 10C.

Specific Heat: Heat capacity per unit mass.

Latent Heat:

Amount of energy transfer per unit mass that does not change the temperature of the body is
called latent heat.

Latent Heat of fusion:

Amount of energy required to change in solid to liquid without changing the temperature of
sample. It is denoted by 𝐿𝑓

Latent Heat of vaporization:

Amount of heat energy required to change a liquid into vapors without changing the
temperature is called latent heat of vaporization.

Sublimation:

Sublimation is the transition of substance directly from solid to the gas or vapors state
without passing through liquid state.

Work: Transfer variable in thermodynamics.

Remember:
 Work is a transfer variable.
 If gas is compress then work is positive And If gas expand then work is negative.
 Work done on the gas is positive.
 Work done by the gas on surrounding is negative.
 Work done in thermodynamic depends upon the initial, final and intermediate states.

 Work done depends upon the path between the states.

Remember:
 Heat is positive, when add to the system And Heat leaving the system is negative.
 Heat depends upon the path b/w states.

First Law of Thermodynamics:

Change in internal energy of system due to energy transfer by heat and work is given by:
∆𝐸𝑖𝑛t = Q+W
Remember:

 Internal energy is the function of state, so it is a state variable And State variables does
not depends on path.

 Internal energy is a microscopic quantity.

 Internal energy does not depends on path.
 First law of thermodynamics is the law of conservation of energy.

 Q-W is referred to work done by the gas.

 Q+W is referred to work done on the gas.

Isothermal process:

A process in which temperature remains constant i.e internal energy does not change.

Adiabatic process:

A process in which net flow of energy is zero i.e heat enters or leaves the system by Q.
Adiabatic process carried out very rapidly so that no heat can enter or leave the system.

∆𝐸𝑖𝑛t = Q+W

---> ∆𝑬 = W
Isobaric process: A process that occurs at constant pressure.

Isochoric process:

A process that occurs at constant volume. Work done in this process is zero in every situation.

Formulas to calculate work done:

Isothermal:

Isobaric process:

Isochoric process: W=0

Adiabatic process:

Remember:

 Internal energy of an ideal gas is a function of temperature only.

 For isochoric process ∆𝐸 = 𝑄

 In adiabatic free expansion ∆𝐸 = 0 As Q=0,W=0
Effects Of Thermal Expansion:
Pendulum clock becomes slower ( Time loss) in summer due to expansion in length by which
Time period increases. Pendulum clock becomes faster (Time gain) in winter due to
contraction in length by which time period decrease. Following formula is used for time gain
1
or lost by pendulum: ΔT = α Δt T » This formula is valid for 1 day problems only.
2

Where α is coefficient of thermal expansion, Δt is difference in temperature and T is time

of the day i.e 86400 seconds.
Calculations in percentage: ΔT/T ×100 (Time diff. ÷ by original time and multiply by 100)
Kinetic Theory Of Ideal Gasses:

Size of molecule << Separation b/w them so we consider them as point particle.
Collision of molecules is perfectly elastic and they follow Newtonian mechanics i.e
equations of motions etc.
Molecules exert forces on each other during collision only.

Pressure of gas:

 Pressure exerted by the ideal gas molecules is directly proportional to the average
translational K.E of gas molecules.

 N/V = No. of molecules per unit volume.

 Pressure of gas depends upon no. of molecules per unit volume.

 Pressure is macro variable and velocity is micro variable so we are connecting
macro state with micro state.

Temperature of gas:
2 1
T= < mv2 >
3𝐾 2
1
T ∝ < mv2 >
2
 Temperature is direct measurement of average K.E
Degree of freedom: In how many different ways system can possess energy.
For example molecules of ideal gas can move in x, y and z axis. So degree of freedom is three.
Equipartition of energy:
1
Each of degree of freedom contributes KT energy of system.
2
For monatomic gas:
𝟏
Eint = 3 degree of freedom × KT
𝟐
For Diatomic gas:
𝟏
Eint = 5 degree of freedom × KT
𝟐
For Polyatomic gas:
𝟏
Eint = 6 degree of freedom × KT = 3 KT
𝟐
Specific Heat For Mono Atomic Gas:

Specific Heat For DiAtomic Gas:

(If vibrational energy included)

Specific Heat For PolyAtomic Gas:

Molecular speed:

Average Speed and most probable speed:

 Remember: < V > > Vrms > Vmp

Mean free path:

The average distance between two collisions is called mean free path. OR Distance
where molecule can move freely is called mean free path.

F stands for frequency of collisions, Should be written as f.

 L is inversely proportional to d2 i.e Mean free path L is less if size of molecules (d) will
be large.
 L is inversely proportional to n i.e Mean free path L is less if No. of molecules (n) are
increases. Because collisions increases.
 L is inversely proportional to v i.e Mean free path L is less if speed of molecules is large.

Remember:

 Lighter molecules of gas can escape more rapidly form earth atmosphere.

 Evaporation is called cooling process.

 Molar specific heat in solid is given by: 𝐶𝑣= 3R
 Internal energy of solid is given by: 𝐸𝑖𝑛𝑡=3𝑛𝑅𝑇
 For monatomic gas translational degree of freedom are three.
 For diatomic gas 3 translation, 2 rotational and two vibration of degree of freedom.
 For polyatomic gas 3 translation, 2 rotational and vibration of degree of freedom.
 Internal energy of ideal gas depend only on temperature.

 Substance like ice is expanded on cooling.

 Specific heat in isothermal process is infinite because change in temp. is zero. Cv= dQ/dT
 Specific heat for adiabatic process is zero. Because dQ = 0 in this process.
 Heat capacity can be negative.(When we remove energy from system to decrease temp.)
 Net Work done is negative if cycle of heat engine operates clockwise and positive if
cycle operates anti clockwise.
Second Law OF Thermodynamics:
Kelvin Statement:

It is impossible to construct a heat engine that extracts heat energy from HTR and converts all of
it into mechanical work and having no sink.

Clausius Statement:

Clausius statement suggests that heat cannot flow itself from cold body to hot body. Some work
should be done.

Remember:

 Zeroth law of thermodynamics concerned with temperature.

 1st law of thermodynamics concerned with internal energy.
 2nd law of thermodynamics concerned with entropy
 Temperature, Internal energy and entropy are all state variables.

Heat Engine:
Device used to convert heat energy into mechanical energy is called heat engine.
Carnot Engine:
The most efficient heat engine is called Carnot heat engine. It was proposed by Carnot in 1824.
Carnot Theorem:
No heat engine can be more efficient than a Carnot engine operating between the same two
temperatures.
Efficiency:
The net amount of work done during a cycle divided by heat input Q H is called thermal
efficiency. e = W / QH
Petrol Engine:
Petrol engine consists of pistons, crankshaft, sparking plug and valves.
Efficiency of petrol engine is not more than 25 to 30 % because of heat and friction losses.
Diesel Engine:
No spark plug is needed in diesel engine. Diesel is sprayed into cylinder at maximum
compression. Efficiency of diesel engine is about 35 to 40 % .
Refrigerator:
Heat engine operating in reverse direction is called refrigerator. The refrigerator extracts heat
from LTR and discharge heat to HTR with the help of work.
Coefficient Of Performance = Desired Heat / Required Work = QL / W
 A good refrigerator has a Coefficient Of Performance cooling b/w 5 , 6.
 If C.O.P = 1 then it means that performance is 100% which is not possible. So COP > 1
 If C.O.P is near to 1 than system has good performance.
Triple Point Of Water:
Temperature at which water, ice and water vapors can exists in equilibrium. By international
agreement this temperature has been defined to 273.16 K.
Reversible process:
The reversible process can return back to its initial state. The carnot cycle is reversible process.
Irreversible process:
The irreversible process cannot return back to its initial state.
All real and natural processes are irreversible processes.

Remember:

 Reversible process is and idealization.

 All natural processes are irreversible.
 A slowly occurs process in thermodynamics equilibrium is almost
irreversible.
 No dissipative effect is present in ideal or irreversible process.
» Energy cannot be converted into friction in ideal or irreversible processes.
Entropy:
Entropy is state variable of thermodynamically system. It was introduced by Rudolph Claudius
in 1856. It is a measure of disorder of molecules of a system. Change in entropy is denoted by
ΔS.
Formula: ΔS = ΔQ / T » For reversible process.
𝒇
Formula: ΔS = ∫𝒊 𝚫𝐐 / T » For irreversible process.

Remember:
 The in entropy is positive (means that entropy increases) when heat is added to system.
 The in entropy is negative (means that entropy decreases) when heat is taken out from
the system.
  Unit of entropy is JK -1
 Entropy of universe increases for all real processes.
 Entropy is zero for irreversible processes.
 Entropy is independent of the path b/w two state because entropy is state variable.
 Entropy is unavailability of mechanical work.

Heat Death Of Universe:

When entropy of universe will reach at maximum value, everything will be at same temperature
and there will be no way to convert heat into useful work and it is called heat death.
Entropy for microscopic scale:

S=𝑘𝑏𝑙𝑛𝑊
» Equation is given by Boltzman. By this equation he connect micro state with macro state.
Heat Transfer:
The flow of thermal energy from hot body to cold body when they are in thermal contact is
called heat transfer. Following are the methods of heat transfer.
Conduction:
The mode of transfer of heat by vibrating atoms and free electrons in solids from hot to cold
parts of the body is called conduction of heat.

» dQ / dT is rate of heat flow which is directly proportional to cross-sectional area of solid

material because larger area contains larger number of molecules and free electrons.
» Rate of heat flow is directly proportional to temperature difference b/w hot and cold parts.
» Rate of heat flow is inversely proportional to length of material because larger length take
more time to conduct heat to the colder end.
Convection:
The transfer of heat by actual movement of molecules from hot place to a cold place is called
convection.
Radiation:
Energy transferred in the form of Electromagnetic waves.
According to Stefan Boltzmann Law, The total energy radiated per second by a material is
proportional to fourth power of absolute temperature of material. It means higher is the
temperature of an object, more it radiates. It also depends on shape and nature of material.
(E = Intensity of radiation)
Emissivity absorptivity:

Emissivity means emission of radiation, And absorptivity means absorption of radiation.

Emissivity e is defined as:
The ratio of the radiant energy emitted by a surface to that emitted by a blackbody at the same
temperature.
» If e = 1, The absorber is ideal absorber and called black body.
» If e = 0, The surface is ideal reflector.
Boyle’s Law:
At constant temperature and constant amount of molecules, Pressure of a gas is inversely
1
proportional to volume. P∝𝑉 OR PV = Constant.
Charles’s Law:
At constant pressure and no. of molecules, Volume of a gas is directly proportional
Temperature.
𝑉
» V∝T OR = Constant.
𝑇
Avogadro’s Law:
At constant temperature and pressure, Volume of gas is directly proportional to no. of molecules.
» V∝N OR V = CN
Grahm’s Law Of Diffusion:
In 1848 Grahm experimentally found that rate of diffusion or effusion of a gas is inversely
proportional to the square root of its molecular mass.

1 1 𝑉1
» V1 = And V2 = By Combining: = √𝑚2/𝑚1
√𝑚1 √𝑚2 𝑉2

Joule Thomson Effect:

The cooling is produced when a gas is allowed to expand through a narrow orifice containing
porous plug is called Joule - Thomson Effect. For this process system should be well insulated.
Enthalpy:
A thermodynamic quantity equivalent to the total heat content of a system is called enthalpy.
Denoted by ‘H’. » H = U + PV
Enthalpy Change: ΔH

i. Exothermic reactions ii. Endothermic reactions

Exothermic Reactions:

An exothermic reaction is a reaction that releases energy to the surroundings. The energy is
released as heat energy.

Endothermic Reactions:

An endothermic reaction is a reaction that absorbs energy from the surroundings. The energy is
absorbed as heat energy.
Thermodynamics Potentials:
Four quantities are called thermodynamics potentials. They are internal energy, enthalpy,
Helmholtz free energy and the Gibbs free energy.

Helmholtz Free Energy:

» F = U – TS Where U is internal energy, T is absolute temperature and S is entropy.

Gibbs Free Energy:

» G = U – TS + PV
Where U is internal energy, T is absolute temperature, S is final entropy, P is absolute pressure
and V is final volume.

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