FISICOQUMICA II

UNIT 1

PHYSICOCHEMICAL PROPERTIES
1.2 Volumetric properties

Beatriz Giner
2015-2016

In this lesson you will

State the difference between bonded and non-bonded interactions
Attribute the type of intermolecular interaction in a pharmaceutical structure

Explain the difference

compressibility of a drug

between

isobaric

thermal

expansion

and

isothermal

Calculate volumetric properties of pharmaceuticals and relate the results with the
molecular structure
Measure the density of drugs in solution
Select the best experimental procedure to measure volumetric properties
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Volumetric properties
Volume and packing
Watch the image. Write three differences regarding the molecular behavior.

Volumetric properties
Volume and packing

FACTORS THAT AFFECT TO THE VOLUME OF A SUBSTANCE

Intermolecular interactions

Short-range intermolecular interactions

Ion-dipole
Ion-induced dipole
Dipole-dipole
Induced dipole-dipole
Induced dipole-induced dipole
(London dispersion forces)

Medium-range intermolecular interactions

Hydrogend bond

Long-range intermoleuclar interactions

Packing
4

Volumetric properties
Volume and packing

Source: http://www.science.uwaterloo.ca/~cchieh/cact/c123/intermol.html

Volumetric properties
Volume and packing
Some definitions
Steric effects are the effects on a chemical or physical property upon the molecular
structure and arise from the fact that a molecule occupies a certain amount of the
available space.
Excluded volume: is the volume that is inaccessible to other molecules in the
system as a result of the presence of the first molecule.
Molar volume: volume occupied by a mole of molecules/atoms. It is always higher
than individual molecular volume. The consequence is the compression of the
matter.
Free molar volume: volume unoccupied by a mole of molecules/atoms. It is also
considered the accessible space for the molecule movement.

Volumetric properties
Volume and packing

Volume depends on several variables: temperature and pressure mainly

EQUATIONS OF STATE

Source: http://www.learnthermo.com/T1-tutorial/ch02/lesson-B/pg05.php

Volumetric properties
Volume and packing
Volume depends on several variables: temperature and pressure mainly
EQUATIONS OF STATE
f n, P,V, T =0

Only one component system:

V=f(T,P)

Real behavior is very complex: USE OF MODELS to simplify

Ideal model for gases
Look for the features of the model

PV=RT for one mole

PV=nRT (for more than one mole)

Only valid for lower

temperatures and
pressures

Volumetric properties
Volume and packing
Volume depends on several variables: temperature and pressure mainly
EQUATIONS OF STATE
f n, P,V, T =0

Only one component system:

V=f(T,P)

Real behavior is very complex: USE OF MODELS to simplify

Van der Waals model for gases
(P+

a
)(Vb)=RT for one mole
V2

a
(P+ V2 )(Vb)=nRT (for more than one mole)
a and b are constants that depend on the
specific gas in question:
a ~ intermolecular interaction strength
b ~ molecular size

9
Source: http://www.ems.psu.edu/~lno/Meteo431/vdWaalc.jpg

Volumetric properties
Volume and packing
Volume depends on several variables: temperature and pressure mainly
EQUATIONS OF STATE
f n, P,V, T =0

Only one component system:

V=f(T,P)

Real behavior is very complex: USE OF MODELS to simplify

Empiric relationships, Virial equation

for GASES
PV=RT+BP+CP2+DP3+

10

Volumetric properties
Volume and packing

As we have just seen, volume depends on temperature and pressure.

V=f(T,P)

Thermal expansion: is the tendency of matter to change in volume in response to a

change in temperature.

The coefficient of isobaric thermal expansion describes how the size of an object
changes with a change in temperature. Several types of coefficients have been
developed: volumetric, area, and linear.
In the general case of a gas, liquid, or solid, the volumetric coefficient of thermal
expansion is given by

Units: K-1

1 V
V =
V T P

High values of V means that the volume of the substance reacts strongly to changes
in temperature.
11

You have just find the relation between temperature and volume of a pharmaceutical
suspension, amoxicillin:
Vm (cm3) = 0.985T2 + 0.334T + 0.121

T (K)

Calculate the thermal expansion coefficient,V , at 298K

REMEMBER: Significant figures of the result?

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Isothermal compressibility: is the tendency of matter to change in volume in response

to a change in pressure.

Isothermal compressibility coefficient describes how the size of an object changes with
a change in pressure and it is defined as:

If pressure increases, volume decreases

Units: Pa-1
High values of kT means that the volume of the substance reacts strongly to changes
in pressure.
13

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Volumetric properties

Density

Mass and volume are extensive properties and are

common for all the matter. These properties depend on
the amount of matter.

Density is a property unique for each substance

Characterization of substances
Relative density of a liquid: ratio between density of the substance and density of
water. Dimensionless

rel

H O

Why the density of

water is 1 g/cm3 ?

Normally, for a substance

solid liquid vapor

Butthis tendency is ALWAYS followed for different substances?

Butthis tendency is ALWAYS followed for the same substance?

15

Volumetric properties

Butthis tendency is ALWAYS followed?

Source: http://www.s-anand.net/blog/calvin-and-hobbes-dad-explains-science/

16

Volumetric properties

Butthis tendency is ALWAYS followed?

Density of liquid water Density of solid water

If density of ice was higher than density of

liquid water, what would happen?

17

Volumetric properties
How to measure the density of a substance?

Source: https://natahenao.wordpress.com/about/hidrostatica-2/

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Volumetric properties
How to measure the density of a substance?
Pycnometer

+
Pycnometer

5.
6.
7.
8.

Balance

1. Measure the weight of the empty pycnometer

2. Fill with distilled water, measure the weight
again.
3. Calculate the weight of water by deducting its
mass inside the pycnometer from the mass of
the pycnometer and find its experimental
density using exp = m/v
4. Calculate correction factor f, by comparison
between experimental density and literature
data (take into account the temperature of the
lab).

Clean the pycnometer. Rinse it with water and let it dry.

Measure the weight of the empty pycnometer
Fill with a liquid sample, measure the weight again.
Calculate the weight of the liquid sample by deducting its mass inside the pycnometer
from the mass of the pycnometer
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9. Calculate experimental density using

Volumetric properties
How to measure the density of a substance?
Pycnometer

Calculate the density of a unknown

substance if a pycnometer of 10.0
0.1 mL of distilled water at 298.15 K
weighted 9.85 g and 10.0 mL of the
unknown substance weighted 9.98 g

Do you know which substance is?

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Volumetric properties
How to measure the density of a substance?
Electronic devices

1. It is possible to measure density and other properties

(speed of sound)
2. High accuracy

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Volumetric properties
Refractive index and molar refraction
c is the speed of light in vacuum

c
T
n =
v

is the speed of light in the medium

Dimensionless

n20 of water at 20C is 1.33

That means that light travels 1.33 times faster in vacuum than in water.
Light travels easier when free molar volume is higher, thus, refractive index decreases.
The LorentzLorenz relationship to obtain Rm, molar refraction:
Rm is the molar refraction

Rm=Vm(n2-1)/(n2+2)

Vm is molar volume
Units of volume

Rm can be interpreted as the hard

core volume of one mole of
molecules
Thus,
Molar free volume = Vm - Rm

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Volumetric properties

Now, after finishing this section, you will draw a mind-map of the main ideas of the
unit. You will have to print it and give to the lecturer.

Mindmap software

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Bibliography
Alexander T Florence, David Attwood. Physicochemical principles of pharmacy,
Pharmaceutical Press, London, 2009
Atkins, P. W. Qumica Fsica. Omega. 1999.
M. Ortuo Marn. Fsica para Biologa, medicina, veterinaria y farmacia. Nuevos
instrumentos universitarios. 1996.
Thomas Engel, Gary Drogny, Philip Reid. Physical Chemistry for the Life Sciences,
Pearson International Edition, 2008