FIRST LAW OF THERMODYNAMICS

THERMODYNAMICS
- Branch of science that deals with relationship of heat and other energy transformations
State Function – Only depends on the initial and final states (PVTUGHAS)
Path Function – only depends on the path (wq)

WORK (w)
- Energy transferred by a system against an opposing force
-Ex. raising a weight against the pull of gravity, expansion of a gas that pushes out a piston, chemical
reaction that drives an electric current through a resistance.

Equation Notes
@ pex = 0 - Is expansion against zero opposing force (pex =
0)
Free o w =0 Work of free expansion
Expansion - That is, no work is done when a system expands
w=0 freely.
- - Expansion of this kind occurs when a gas
expands into a vacuum.
@pex = constant - The work arising from a change in volume
o + w expansion
o -w compression
- The force acting on the piston, pexA, is
equivalent to the force arising from a weight
that is raised as the system expands.
- It is important to note that it is still the external
pressure that determines the magnitude of the
Expansion work.
Against - However, when a gas is compressed, the ability
Constant of the surroundings to do work is diminished by
Pressure an amount determined by the weight that is
lowered, and it is this energy that is transferred
into the system.

Indicator Diagram -A pV-graph used to illustrate

expansion work : James Watt first used one to
indicate aspects of the operation of his steam
engine.

Reversible @ pex = pgas Reversible Change - a change that can be reversed

Expansion by an infinitesimal modification of a variable.

The key word ‘infinitesimal’ sharpens the everyday

meaning of the word ‘reversible’ as something that
can change direction.
“Systems at equilibrium are poised to undergo
reversible change”

Mechanical equilibrium
- Ex. Suppose a gas is confined by a piston
and that the external pressure, pex, is set equal to
the pressure, p, of the confined gas.
o If the external pressure is reduced
 infinitesimally, the gas expands slightly.
o If the external pressure is increased
infinitesimally, the gas contracts slightly
- System is in mechanical equilibrium with its
surroundings because an “infinitesimal change in
the external pressure in either direction causes
changes in volume in opposite directions.”
- In either case the change is reversible in
the thermodynamic sense.
@ pex = pgas - The expansion is made isothermal by keeping
the system in thermal contact with its
surroundings (which may be a constant
temperature bath).
- When the Vfinal > VInitial = - w.
o In this case, the system has done work
on the surroundings and there is a
corresponding negative contribution
to its internal energy.
- ↑T↑P↑w
- More work is obtained when the expansion is
reversible (the area is greater) because
matching the external pressure to the internal
Isothermal
pressure at each stage of the process ensures
reversible
that none of the system’s pushing power is
expansion
wasted.
- We cannot obtain more work than for the
reversible process because increasing the
external pressure even infinitesimally at any
stage results in compression.
- We may infer from this discussion that,
because some pushing power is wasted when
p > pex, the maximum work available from a
system operating between specified initial and
final states and passing along a specified path
is obtained when the change takes place
reversibly.

- the external pressure differs measurably

from the internal pressure, then changing
pex infinitesimally will not decrease it
below the pressure of the gas, so will not
Irreversible
change the direction of the process.
Expansion
- Such a system is not in mechanical
equilibrium with its surroundings and the
expansion is thermodynamically
irreversible.

- Because the expansion is adiabatic, we

know that q = 0; then because ΔU = q +
w, it follows that ΔU = wad (‘ad’ denotes
an adiabatic process).
Work of
- That is, the work done during an adiabatic
Adiabatic
expansion of a perfect gas is
Change
proportional to the temperature
difference between the initial and final
states.
 Where, . This results is
commonly summarized in the form :

3
For a monatomic perfect gas, CV,m = R and
2
5 5
Cp,m = R (from Cp,m − CV,m = R), so γ = .
2 3
For a gas of nonlinear polyatomic molecules
(which can rotate as well as translate;
vibrations make little contribution at normal
temperatures): CV,m = 3R and Cp,m = 4R, so γ =
4
.
3

Perfect Gas
That
Undergoes
Reversible
Adiabatic
Expansion

and one for a reversible path is illustrated Because γ > 1, an adiabat falls more steeply (p ∝ 1/Vγ
Adiabats - The curves of pressure versus volume for adiabatic change are known as adiabats,

) than the corresponding isotherm (p ∝ 1/V).

- The physical reason for the difference is that, in an isothermal expansion, energy flows into
the system as heat and maintains the temperature; as a result, the pressure does not fall as
much as in an adiabatic expansion.

HEAT
- Energy transferred by a system through temperature differences.
- In molecular terms, heating is the transfer of energy that makes use of disorderly, apparently
random, molecular motion in the surroundings.
Boundaries
- Not all boundaries permit the transfer of energy even though there is a temperature difference
between the system and its surroundings.
1. Diathermic - Boundaries that do permit the transfer of energy as heat.
2. Adiabatic - those that do not permit the transfer of energy as heat.
Exothermic vs Endothermic
A. Exothermic process
- Is a process that releases energy as heat into its surroundings.
- All combustion reactions are exothermic.
B. Endothermic process
- is a process in which energy is acquired from its surroundings as heat.
!! Heat is a process (the transfer of energy as a result of a temperature difference), not an entity!!

Adiabatic
When an endothermic process takes place in an adiabatic container, it results in a lowering of
temperature of the system
An exothermic process results in a rise of temperature.
a) When an endothermic process occurs in an adiabatic system, the temperature falls;
(b) if the process is exothermic, then the temperature rises.

Diathermic
An endothermic process in a diathermic container result in energy flowing into the system as heat to
restore the temperature to that of the surroundings.
An exothermic process in a similar diathermic container result in a release of energy as heat into the
surroundings.
(c) When an endothermic process occurs in a diathermic container, energy enters as heat from the
surroundings, and the system remains
at the same temperature.
(d) If the process is exothermic, then energy leaves as heat, and the process is isothermal.

Thermal Motion - The disorderly motion of molecules.

work is identified as energy transfer making use of the organized motion of atoms in the
surroundings
heat is identified as energy transfer making use of thermal motion in the surroundings.
ENERGY
- Capacity of a system to do work.
-When work is done on an otherwise isolated system (+w) the capacity of the system to do work is
increased; in other words, the energy of the system is increased.
- When the system does work (-w), the energy of the system is reduced and it can do less work than
before.
Experiments have shown that the energy of a system may be changed by means of:
a. Work
b. Temperature change/Heat
When the energy of a system changes as a result of a temperature difference between the system and its
surroundings we say that energy has been transferred as heat.

--------------------------------------------------------------------------------------------------------------------
ZEROTH LAW OF THERMODYNAMICS
“If A and B are in thermal equilibrium and A and C are in thermal
equilibrium, then B and C are also in thermal equilibrium”
- The Zeroth Law justifies the concept of temperature and the use
of a thermometer, a device for measuring the temperature.
- One application is thermometry.

FIRST LAW OF THERMODYNAMICS

“The internal energy of an isolated system is constant.”
Similar to Law of Conservation of Energy

Internal Energy (U)

- the total kinetic and potential energy of the constituents (the atoms, ions, or molecules) of the
system / Total energy of the system.
- Dependent on volume and temperature:

For an isolated system:

∆U = 0
For a closed system:
∆U = q + w
For a open system:
∆U = q + w + ∆E

- is a state function in the sense that its value depends only on the current state of the system
and is independent of how that state has been prepared.
- The internal energy is an extensive property of a system (a property that depends on the
amount of substance present)

kinetic energy forms • symmetric stretching

• bending • asymmetric stretching
 • rotational motion Potential Energy Forms
• translational motion (linear) • Intramolecular potential
• Intermolecular potential

Molar Internal Energy (Um)

- is the internal energy divided by the amount of substance in a system.

Um = U/n SI: kJ/mol

- it is an intensive property (a property independent of the amount of substance)

-That is, the internal energy of a perfect gas is independent of the volume it occupies.

HEAT TRANSACTIONS
dU = dq Heat transferred at constant volume

CALORIMETRY
Calorimetry
- Science of measuring heat
- is the study of the transfer of energy as heat during
physical and chemical processes.
Calorimeter
- device for measuring energy transferred as heat.
- The most common device for measuring q V (and
therefore ΔU) is an adiabatic bomb calorimeter
- The change in temperature, ΔT, of the calorimeter is proportional to the energy that the
reaction releases or absorbs as heat.
- Therefore, by measuring ΔT we can determine qV and hence find ΔU.

- The calorimeter constant may be measured electrically by passing a constant current, I, from a
source of known potential difference, Δϕ, through a heater for a known period of time, t, for
then:
q = It Δϕ

Isobaric Calorimeter

- A calorimeter for studying processes at constant pressure.

- A simple example is a thermally insulated vessel open to the atmosphere: the heat released in
the reaction is monitored by measuring the change in temperature of the contents.
 Adiabatic Flame Calorimeter

- For a combustion reaction an adiabatic flame calorimeter may be used to measure ΔT when a
given amount of substance burns in a supply of oxygen .
- Another route to ΔH is to measure the internal energy change by using a bomb calorimeter, and
then to convert ΔU to ΔH.

- Because solids and liquids have small molar volumes, for them pV m is so small that the molar
enthalpy and molar internal energy are almost identical:
Hm = Um + pVm ≈ Um
- Consequently, if a process involves only solids or liquids, the values of ΔH and ΔU are almost
identical.
- Physically, such processes are accompanied by a very small change in volume; the system does
negligible work on the surroundings when the process occurs, so the energy supplied as heat stays
entirely within the system.

HEAT CAPACITY

- The amount of energy needed to raise the temperature of a certain amount of substance by a
degree.
- Heat capacities are extensive properties.

- Because a change in enthalpy can be equated with the energy supplied as heat at constant
pressure, the practical form of the latter equation is :

- The variation of heat capacity with temperature can sometimes be ignored if the temperature
range is small; this approximation is highly accurate for a monatomic perfect gas (for instance,
one of the noble gases at low pressure).

- The empirical parameters a, b, and c are independent of temperature and are found by fitting
this expression to experimental data.

Molar heat capacity at constant volume, C V,m - is the heat capacity per mole of substance, and
is an intensive property (all molar quantities are intensive), C V,m for polyatomic gases are close
to 25 J K−1 mol−1.

Specific heat capacity/ ‘specific heat’ - is the heat capacity of the sample divided by the mass,
usually in grams.

- The heat capacity is used to relate a change in internal energy to a change in temperature of a
constant-volume system

dU =CVdT Constant volume

- Can be molar (per mole) or specific (per mass)

Infinite Heat Capacity

- An infinite heat capacity implies that there will be no increase in temperature however much
energy is supplied as heat.
- At a phase transition, such as at the boiling point of water, the temperature of a substance
does not rise as energy is supplied as heat: the energy is used to drive the endothermic
transition, in this case to vaporize the water, rather than to increase its temperature.
- Therefore, at the temperature of a phase transition, the heat capacity of a sample is infinite.

Relation between the two heat capacities of a perfect gas:

Cp − CV = nR

It follows that the molar heat capacity of a perfect gas is about 8 J/ K mol larger at constant
pressure than at constant volume.

ENTHALPY

- It is the total heat content of the system; sum of

internal energy and pressure multiplied by volume.
- A change in enthalpy is equal to the energy
transferred as heat at constant pressure.

dH = dqp Heat transferred at constant pressure

- Enthalpy is a state function too.
- Dependent on temperature and pressure

Isothermal JT Coefficient

- ZERO if ideal gas

- Has an expression for real gas

Enthalpy of a Perfect Gas

- is related to its internal energy by using pV = nRT .

THERMOCHEMISTY
- The study of heat changes accompanying chemical reactions

Standard Enthalpy Change(ΔHᶿ )

- The change in enthalpy for a process in which the initial and final substances are in their standard
states.

The standard state of a substance at a specified temperature is its pure form at 1 bar.
- ΔHᶿ is the change in enthalpy when reactants in their standard states change to products in their
standard states:

Pure, separate reactants in their standard states

→pure, separate products in their standard states

Standard Enthalpy of Reaction(ΔrH0)

Standard Enthalpy of Combustion (Δ c H0) – standard reaction enthalpy of reaction specific for
combustion; expressed in terms of 1 mole burnt substance

Standard Enthalpy of Transition (ΔtrsHᶿ ) - Standard enthalpy change that accompanies a change of
physical state.

Standard Enthalpies of Formation (Δ fHᶿ ¿ - Standard reaction enthalpy for the formation of the
compound from reference states (most stable form at standard conditions (must be in their elemental
form))

“The reference state of an element is its most stable state at the specified temperature and 1 bar.”

- Standard enthalpies of formation are expressed as enthalpies per mole of molecules or (for ionic
substances) formula units of the compound.
- The standard enthalpies of formation of elements in their reference states are zero at all
temperatures because they are the enthalpies of such ‘null’ reactions as N2(g) → N2(g).

Lattice Enthalpy (ΔHL)

- Is the change in standard molar enthalpy for this process.

- The lattice enthalpy is equal to the lattice internal energy
at T = 0; at normal temperatures they differ by only a few
kilojoules per mole, and the difference is normally
neglected.
- Experimental values of the lattice enthalpy are obtained
by using a Born–Haber cycle, a closed path of
transformations starting and ending at the same point,
one step of which is the formation of the solid compound
from a gas of widely separated ions.

Thermochemical Equation - A combination of a chemical equation and the corresponding change in

standard enthalpy.

Hess’s Law

- “The standard enthalpy of an overall reaction is the sum of the standard enthalpies of the individual
reactions into which a reaction may be divided.”

The Temperature Dependence of Reaction Enthalpies

THE JOULE-THOMSON EXPERIMENT

- The study of the dependence of the energy and enthalpy of real gases on volume (pressure) was
done by Joule in association with Thomson who devised a different procedure. They allowed gas to
expand freely through a porous plug, or frit.

Joule-Thomson effect also known as Kelvin–Joule effect or Joule-Kelvin effect is the change in fluid’s
temperature as it flows from a higher-pressure region to lower pressure. The basic principle of Joule
Thomson effect is based on the transfer of heat. Also, at ordinary temperature and pressure, all real
gases undergo expansion and this phenomenon is used in the process of liquefying gases. But this does
not hold good for hydrogen and helium.

PHASE CHANGES

Phase transformations occur at constant pressure

Sensible heat

Heat accompanying temperature change

Latent Heat

Heat accompanying phase change

Constant Phase Value

Specific Heat Capacities (cal/goC) at 1 Ice 0.50

atm Liquid water 1.00

Steam 0.48

Specific Enthalpy of Phase change (cal/g) Fusion 80

at 1 atm
Vaporization 540