Physical Chemistry: study of the fundamental physical principles

that control the chemical systems (“the Physics of Chemistry”)

Equilibrium Change Structure

Macroscopic and microscopic viewpoints

Statistical Mechanics
(micro, macro,
equilibrium+change)

Quantum Chemistry and

Thermodynamics
Spectroscopy
(macro,
(micro, structure)
equilibrium)

Chemical Kinetics
(micro, macro, change)
 Part I: Thermodynamics
Chapter 1: The first law

– Fundamentals of Thermodynamics
– The first law of TD
– Physical changes
– Chemical changes

Bibliography
• Chang, R. “Fisicoquímica”, chap. 4
• Atkins, P. “Physical Chemistry for the Life Sciences”, chap. 0 and 1
Thermodynamics

• Transformation of energy

• Properties at the equilibrium of a system, at a macroscopic level

• (Britannica) Science of the relationship between heat, work,

temperature, and energy

Different approaches to TD:

– Engineers (mechanical, chemical)

– Physicists
– Chemists
– Life sciences: biochemistry, medicine, pharmacy
Work = movement against a force (no movement, no work)

Energy = capacity to perform work

System: part of the universe under study

Diathermal wall

Adiabatic wall
Temperature = a measure of the (kinetic) energy of the
molecules (warm, cold)

T determines the heat flux (= energy flux): “Zeroth Law of TD”

Absolute scale (Kelvin) T =  (ºC) + 273.15

Celsius scale: 0ºC (fusion H2O) -100ºC (boiling), 1 atm
Maxwell-Boltzmann velocity distribution

2 3RT
v 
M

1 2 3RT
Ec  mv 
2 2
Heat (Q): The transfer of energy from one
body to another as a result of a difference
in temperature

Q and W are different forms of transfer

of energy

Ej: combustion
of urea in a
cylinder: energy
leaves the
system as
Q+W

At a molecular level: W = orderly motion; Q = random motion

Sign convention in TD

W, Q > 0 when the system gains in

energy (energy ENTERS the system)

W, Q < 0 when the system losses

energy (energy LEAVES the system)

Exothermic process: PRODUCES HEAT

(to the surroundings)

Endothermic process: ABSORBS HEAT

(from the surroundings)
Extensive properties: DEPEND on the amount of
substance (number of particles). EP are additive

e.g.: 1 kg of water - 2 kg of water > V, mass are extensive

Intensive properties: DO NOT DEPEND on the amount of

substance. IP are not additive

e.g.: T, P

We can easily convert some extensive properties into

intensive ones:
ej: density =m/V
specific volume v=1/=V/m
Molar properties
Intensive (obtained by dividing by the number of moles)

Vm = = V / n (volume / moles of substance)

e.g. = RT/P

Equation of state
The state of a (thermodynamic) system can be described
just by 4 variables: P, V, n, T

These variables of state are connected (e.g. P = f (V,T,n))

If we know 3 of them the 4th is automatically defined

PV = nRT
Heat capacity

Q
C
T
C / mass = Cs (specific heat capacity)

C / mol = Cm or 𝐶 (molar heat capacity)

It can be measured at constant P or V

𝐶 𝑃 𝐶𝑉
Thermodynamic processes

state A (Pi ,Vi, Ti)  state B (Pf, Vf, Tf)

• Isothermal, isochoric, isobaric, adiabatic

• Reversible and irreversible processes

Reversible processes: occur through an infinite number of

equilibrium steps (ideal processes)

Irreversible process: not reversible

Example. Work in an isothermal expansion

(W done by the system when it expands against

an external and constant pressure, at constant T)

W = - PexV
Wirrev < Wrev  the path matters…
The first law of TD

“Conservation of energy”
“The internal energy is constant in an isolated system”
E is a function of state (independent on the
E  Q  W path) and extensive

dE  dQ  dW W and Q are not functions of state (e.g.: iso-

thermal expansion of a gas), Q, W

hard way
E=mgh
hiking the “Higa de
easy way Monreal”

the path matters!

Enthalpy
2C57H110O6(s) +163O2(g)  114 CO2(g) +110H2O(l)

Change in volume corresponding to

n = np - nr = 114 - 163 = - 49 mol of gas per 2 of
tristearin

CaCO3(s) + Q  CaO(s) + CO2(g)

n = +1 mol of gas per 1 of Ca carbonate

It is more convenient to define a magnitude that represents

the heat evolved (either released or absorbed) at
constant pressure
H = E + PV
H is a function of state, and extensive (like E). It is intensive
when given per mol:
𝐻= 𝐸+𝑃 𝑉
Examples: TD processes in (ideal) gases
Isochoric: V = 0
dW   PdV  0
dE  dQ
Isothermal: T = 0 and E = 0 (ideal gas: E only depends on T)
dQ   dW  PdV
Isobaric: P = 0

dE  dQ  dW  dQ  PdV
dH  dE  PdV
Adiabatic: Q = 0 (no heat exchange with the surroundings)

dE  dW
Physical changes

3 states of matter (S,L,G)

Solids: may present different

phases: state of matter that is
uniform in composition and in
physical state (ex: 12 ph. in ice!)
Intermolecular forces

Van der Waals: weak (ca. 2 kJ/mol)

- Dipole-dipole, ion dipole, ion-ion,…
- London (transient induced dipoles)

Hydrogen bonding: directional, intense (ca. 20 kJ/mol)

 London forces depend
on the molar mass
(more electrons) and
the molecular shape

non-polar molecule
 Hydrogen bonding (H bound to O, N, F)

DNA

Cellulose

- Interactions along the tetrahedron axes

- Stronger than dipole-dipole
 Chemical changes

H    bonds broken   bonds formed

Break = +Q (endo)

Form = -Q (exo)
Combustions and biological fuels

• Given as positive
(although Q<0, always)

• Specific enthalpy (Qc per

gram)

• Enthalpy density (Qc per

liter). Good for liquids and
gases

• Lipids > carbohydrates =

proteins
Enthalpy of formation

r H o    p H o (products)    r H o (reactants)
 Standard state (reference state) of a compound: its thermodynamically most
stable state at 1 bar at a given temperature (normally 25ºC)
 Enthalpy of formation: the H for the reaction of formation of 1 mol of
compound from its constituents, in their standard states
 Hess’ law: the total enthalpy in a chemical reaction is the same whether the
reaction takes place in one or in several steps

r H o    p H of (products)    r H of (reactants)

“enthalpy of formation”

(tabulated in
Thermodynamic tables
for a number of
compounds)
Kirchhoff’s law (dependence of H with T)
Tf


 r H o (T f )   r H o (Ti )   r C Po dT
Ti

Normally Cp does not change much

over the T interval considered, hence

 r H o (T f )   r H o (Ti )   r C Po T

For practical purposes (biochemical

rections), H does not depend much
on T (exceptions: structural changes
in biopolymers)
Examples

1. For the combustión of solid glycine, calculate:

a) The molar and specific enthalpies of combustión

b) The change in the internal energy of the reaction

2. Consider the formation of glutamine from the reaction of glutamate

and ammonium in aqueous solution under SATP conditions.
Calculate the enthalpy of the reaction at 60ºC
Key concepts of the chapter
 Work and energy
 Systems and walls
 Temperature and heat, sign convention
 Ideal gases and speed distribution
 Extensive, intensive, molar properties
 Heat capacity: meaning, definitions
 Reversible and irreversible processes
 First law: mathematical formulation, implications
 TD processes in ideal gases
 Enthalpy
 State and phase, standard state, changes of phase
 Intermolecular forces
 Chemical changes: Bonds and reactions
 Combustions and biological fuels
 Enthalpies of formation, Hess’s law
 Variation of the enthalpy with T (Kirchhoff’s law)