FISICOQUÍMICA BÁSICA

(BASIC PHYSICAL CHEMISTRY)

DR. VÍCTOR MANUEL BAIZABAL AGUIRRE

LICENCIATURA INSTITUCIONAL EN BIOTECNOLOGÍA

SEMESTRE I

2018-2019
WHY CHEMISTRY IS SO IMPORTANT?
CHEMISTRY IS DIVIDED INTO 5 MAJOR AREAS:
HOW CAN WE DEFINE PHYSICAL CHEMISTRY?
The branch of chemistry concerned with
the application of the techniques and
theories of physics to the study of
chemical systems.
 LOS SISTEMAS BIOLÓGICOS SE PUEDEN DEFINIR COMO UNA
Colección de reacciones químicas interconectadas que están reguladas
de manera espacial y temporal

p.ej. Crecimiento, reproducción, movimiento, pensamiento, etc)

SIN EMBARGO, EXISTEN RESTRICCIONES FÍSICAS Y QUÍMICAS SOBRE LOS SISTEMAS BIOLÓGICOS

 Propiedades químicas de los elementos.

Estas propiedades limitan el tipo de moléculas que un
organismo puede sintetizar.
 Requerimientos energéticos de las reacciones químicas.
Balance entre la energía disponible del entorno y la
necesidad de energía en las células.
 Velocidad de las reacciones químicas.
Además de ser espontánea, las reacciones deben ocurrir a velocidades
compatibles con los procesos fisiológicos.
¿Quieren realmente estudiar cómo la materia y la
energía están interconectadas?

I hate that kind of

questions…
…$#%&

Not that I want, I

have to...
 Si tu repuesta fue SI, NO o NO SÉ,
en cualquier caso debes desarrollar buena habilidad en MATEMÁTICAS

¡¡I thought biotechnology had

nothing to do with Maths!!
THE THREE STATES OF MATTER
GAS PRESSURE AND ITS MEASUREMENT
A mercury barometer

Why do laboratory barometers contain

mercury instead of water?
TWO TYPES OF MANOMETER
UNITS OF PRESSURE
THE RELATIONSHIP BETWEEN VOLUME AND PRESSURE: BOYLE’S LAW
THE RELATIONSHIP BETWEEN VOLUME AND TEMPERATURE CHARLES’S LAW

Charles’s law: at constant pressure, the volume occupied by a

fixed amount of gas is directly proportional to its absolute (Kelvin)
temperature
OTHER RELATIONSHIPS BASED ON BOYLE’S AND CHARLES’S LAWS
at constant volume, the pressure exerted by a fixed amount of gas is
directly proportional to the absolute temperature:
 THE RELATIONSHIP BETWEEN VOLUME AND AMOUNT:
AVOGADRO’S LAW

Conclusion and statement of the law. Thus, at fixed temperature and pressure, the volume occupied by a
gas is directly proportional to the amount (mol) of gas:
GAS BEHAVIOR AT STANDARD CONDITIONS
standard temperature and pressure (STP):
STP: 0°C (273.15 K) and 1 atm (760 torr)

Under these conditions, the volume of 1 mol of an ideal gas is

called the standard molar volume:
Standard molar volume = 22.4141 L or 22.4 L
 THE IDEAL GAS LAW
∙ Boyle’s law focuses on pressure (V ∝ 1/P).
∙ Charles’s law focuses on temperature (V ∝ T).
∙ Avogadro’s law focuses on amount (mol) of gas (V ∝ n).

By combining these individual effects, we obtain the ideal gas

law (or ideal gas equation):

V ∝ nT/P or PV ∝ nT or PV = constant × nT or PV/nT = R

where R is a proportionality constant known as the universal gas

constant. Rearranging gives the most common form of the ideal
gas law:
PV = nRT

Calculate the value of R from STP values

When initial conditions (subscript 1) change to final
conditions (subscript 2), we have:

Problemas…1-15
 THE DENSITY OF A GAS
Differences in gas density (d = m/V) depend on differences in molar mass

the number of moles (n) is the mass of substance (m) divided by

its molar mass (ℳ), n = m/ℳ

∙ The density of a gas is directly proportional to its molar mass.

∙ The density of a gas is inversely proportional to the temperature.

∙ The density of a gas is directly proportional to the pressure.

Problemas…16 y 17
 THE MOLAR MASS OF A GAS

…another rearrangement of the ideal gas law

Problemas…I-III
 THE KINETIC-MOLECULAR THEORY: A MODEL FOR GAS BEHAVIOR
The kinetic-molecular theory is the model that accounts for macroscopic gas behavior
at the level of individual particles (atoms or molecules). James Clerk Maxwell and
Ludwig Boltzmann.
Questions Concerning Gas Behavior
1. Origin of pressure. Pressure is a 2. Boyle’s law (V ∝ 1/P). A change in
measure of the force a gas exerts on a gas pressure in one direction causes a
surface. How do individual gas change in gas volume in the other.
particles create this force? What happens to the particles when
3. Dalton’s law (Ptotal = P1 + P2 +
external pressure compresses the gas
P3 + · · ·). The pressure of a gas
volume? And why aren’t liquids and
mixture is the sum of the pressures of
solids compressible?
the individual gases. Why does each
gas contribute to the total pressure in
proportion to its number of particles?

4. Charles’s law (V ∝ T). A change in

temperature causes a corresponding change 5. Avogadro’s law (V ∝ n). Gas volume depends
in volume. What effect does higher on the number of moles present, not on the
temperature have on gas particles that chemical nature of the gas. But shouldn’t 1 mol
increases gas volume? This question raises of heavier particles exert more pressure, and
a more fundamental one: what does thus take up more space, than 1 mol of lighter
temperature measure on the molecular ones?
scale?
 POSTULATES OF THE KINETIC-MOLECULAR THEORY

Postulate 1. Particle volume. A gas consists of

a large collection of individual particles with
empty space between them. The volume of
each particle is so small compared with the
volume of the whole sample that it is assumed
to be zero; each particle is essentially a point Postulate 2. Particle motion. The particles are in
of mass. constant, random, straight-line motion, except
when they collide with the container walls or
with each other.

Postulate 3. Particle collisions. The collisions are elastic,

which means that, like minute billiard balls on a frictionless
billiards table, the colliding molecules exchange energy but
do not lose any energy through friction. Thus, their total
kinetic energy (Ek) is constant. Between collisions, the
molecules do not influence each other by attractive or
repulsive forces.
Each particle has a molecular speed (u); most are moving near the most probable speed,
but some are much faster and others much slower.

∙ the curves flatten and spread at higher temperatures

∙ the most probable speed (the peak of each curve) increases as the
temperature increases.
The increase in most probable speed occurs because
Ek ∝ T or Ek = c × T
Conclusion: at a given temperature, all gases have the
same average kinetic energy.
 A MOLECULAR VIEW OF THE GAS LAWS
1. Origin of pressure. From postulates 1 and 2, each gas particle (point of mass)
colliding with the container walls exerts a force.

Countless collisions over the inner surface of the container result in a

pressure.

The greater the number of particles, the more frequently they collide with the
container, and so the greater the pressure.

Pressure arises from countless

collisions between gas particles and
walls.
2. Boyle’s law (V ∝ 1/P) The particles in a gas are points of
mass with empty space between them (postulate 1).

Before any change in pressure, the pressure exerted by

the gas (Pgas) equals the pressure exerted on the gas
(Pext), and there is some average distance (d) between
the particles and the container walls.
The fact that liquids and solids cannot be compressed
implies there is little, if any, free space between their
particles.
 3. Dalton’s law of partial pressures

Adding a given amount (mol) of
gas A to a given amount of gas
B causes an increase in the
total number of particles, in
proportion to the particles of A
added.
This increase causes a Each gas exerts a fraction of P in
corresponding increase in the proportion to its fraction of the
total number of collisions with total number of particles (or
the walls per second (postulate equivalently, its fraction of the
2), which causes a corresponding total number of moles, that is,
increase in the total pressure of the mole fraction).
the gas mixture (P).

At some starting temperature,
T, the external (atmospheric)
pressure (Patm) equals the
pressure of the gas (Pgas).
4. Charles’s law (V ∝ T)
When the gas is heated and the
temperature increases to T2, the
most probable molecular speed
and the average kinetic energy
increase (postulate 3).
Thus, the particles hit the walls more
frequently and more energetically. This change
temporarily increases P. As a result, the piston
moves up, which increases the volume and
lowers the number of collisions with the walls
until Patm and Pgas are again equal.
 5. Avogadro’s law (V ∝ n)

At some starting amount, n
equals Pgas. When more gas is
added from the attached tank,
the amount increases to n.
Thus, more particles hit the walls more
frequently, which temporarily increases
P. As a result, the piston moves up, which
increases the volume and lowers the
number of collisions with the walls.
THE CENTRAL IMPORTANCE OF KINETIC ENERGY
Why don’t the heavier O2 molecules, which strike the container
walls with more force than the lighter H2 molecules, exert more
pressure and thus take up more volume?
1. Key implication of Avogadro’s law.

lighter molecules move faster, on average, than heavier molecules.

An object’s mass and speed are inversely related: a heavy

object moving slower can have the same kinetic energy as a
light object moving faster.
 2. THE MEANING OF TEMPERATURE.

temperature is a measure of the average kinetic energy

of the particles: as T goes up, Ek increases, and as T
goes down, Ek decreases.
 ROOT-MEAN-SQUARE SPEED
The average kinetic energy of each particle in a large population is

Setting this expression for average kinetic energy equal to the earlier one gives

Multiplying through by Avogadro’s number

gives the average kinetic energy for a mole of gas
particles:

Avogradro’s number times the molecular mass, NA x m, is

the molar mass M, and solving for u2, we have
rms speed (u): a particle
moving at this speed has the
average kinetic energy.
Urms = 1.09 × average speed
 Problema

Calculate the root-mean-square speed of an O2 molecule (M = 3.200×10-2 kg/mol) at

room temperature (20°C, or 293 K) in the air you’re breathing.

Problemas…
 THE PROCESS OF DIFFUSION
Graham’s law:

Lighter molecules have higher average speeds than

heavier molecules, so they move farther in a given time.
Diffusion of gases. Different gases (black, from the left, and green,
from the right) move through each other in a tube and mix. For
simplicity, the complex path of only one black particle is shown (in
red). In reality, all the particles have similar paths

If gas molecules move at hundreds of meters per second,

why does it take a second or two after you open a bottle
of perfume to smell it?
 MEAN FREE PATH

The average distance it travels between collisions at a given temperature and

pressure.
At 20°C and 1 atm pressure, the N2 molecule is traveling at an average speed of
470 m/s (rms speed = 510 m/s), or nearly 1760 km/h!
The N2 molecule (3.7×10−10 m in diameter) has a mean free path of 6.6×10−8
m, which means it travels an average of 180 molecular diameters before
smashing into a fellow traveler.

To match the collision

frequency of the N2 molecule,
you would need to be
traveling in a bumper car at
4.5 billion km/s, much faster
than the speed of light! and
would smash into another
bumper car every 640 m.
Notas (pp45)

Problema (pp48)
 COLLISION
FREQUENCY
It is the most probable speed (meters per second) divided by the mean
free path (meters per collision)
The average number of collisions per second that each particle
undergoes, whether with another particle or with the container.
N2 molecule

Distribution of speed (and

kinetic energy) and collision
frequency are essential ideas for
understanding the speed of a
reaction.
REAL GASES: DEVIATIONS FROM IDEAL BEHAVIOR
1. Gas particles are not points of mass with zero volume.

2. Attractive and repulsive forces do exist among gas particles.

These two features cause deviations from ideal behavior under

extreme conditions of low temperature and high pressure.

High pressure. As Pext rises, the volume of the sample decreases and the
particles get closer together, so interparticle attractions have a greater effect.

The effect of interparticle attractions on measured gas pressure.

Low temperature. Lowering the temperature slows the particles, so
they attract each other for a longer time.

The interparticle attractions cause the gas particles to lose

enough kinetic energy that they condense to a liquid.

Effect of particle volume. At normal Pext, the space

between particles (free volume) is enormous.

At moderately high Pext and as free volume decreases,

the particle volume makes up an increasing proportion
of the container volume.

At extremely high pressures, the space taken up by the

particles themselves makes the free volume significantly
less than the container volume.
The effect of particle volume on measured gas volume.
 THE VAN DER WAALS EQUATION:
ADJUSTING THE IDEAL GAS LAW
1. Adjust P up by adding a factor that accounts for interparticle
attractions.

2. Adjust V down by subtracting a factor that accounts for

particle volume.

At ordinary conditions, the van

der Waals equation becomes the
ideal gas equation.

Johannes van der Waals (1873)

a and b are van der Waals constants

The constant a depends on the number and distribution of electrons,
which relates to the complexity of a particle and the strength of its
interparticle attractions.

The constant b relates to particle volume.

Values of the van der Waals constants for
some common gases

Problemas…