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van 't Hoff factor (named after J. H.

van 't Hoff) is a


measure of the effect of a solute upon colligative
properties such as osmotic pressure, relative
lowering in vapor pressure, elevation of boiling
point and freezing point depression. The van 't Hoff
factor is the ratio between the actual concentration
of particles produced when the substance is
dissolved, and theconcentration of a substance as
calculated from its mass. For most nonelectrolytes dissolved in water, the van' t Hoff factor
is
essentially
1.
For
most ionic
compounds dissolved in water, the van 't Hoff factor
is equal to the number of discrete ions in a formula
unit of the substance. This is true for ideal
solutions only, as occasionally ion pairing occurs in
solution. At a given instant a small percentage of
the ions are paired and count as a single particle.
Ion pairing occurs to some extent in all electrolyte
solutions. This causes deviation from the van 't Hoff
factor. The deviation for the van 't Hoff factor tends
to be greatest where the ions have multiple
charges.
Dissociated solutes[edit]
The degree of dissociation is the fraction of the
original solute molecules that have dissociated. It
is usually indicated by the Greek symbol . There is
a simple relationship between this parameter and

the van't Hoff factor. If a fraction of the solute


dissociates into ions, then

For example, the dissociation


KCl K+ + Clyields

particles, so that

Associated solutes[edit]
Similarly, if a fraction of moles of solute
associate to form one mole of an n-mer (dimer,
trimer, etc.), then
For the dimerisation of acetic acid in benzene
2CH3COOH (CH3COOH)2
2 moles of acetic acid associate to form 1
mole of dimer, so that

Physical significance of [edit]

Dimerization of a carboxylic acid by


formation of hydrogen bonds (shown
as dotted lines).

When solute particles associate in


solution,
is less than 1. For
example,carboxylic acids such as
ethanoic acid (acetic acid) or benzoic
acid form dimersin benzene, so that
the number of solute particles is half
the number of acid molecules.

When solute particles dissociate in


solution,
is greater than 1.
(e.g. sodium
chloride
in
water, potassium
chloride in
water, magnesium chloride in water)
When
solute particles neither
dissociate
nor
associate
in
solution, equals 1. (e.g. Glucose in
water)
The value of is ; = the actual number of
particles in solution after dissociation
the number of formula units initially
dissolved in solution. Means the number
of particles per formula unit of the solute
when a solution is dilute.

Association

of

Molecules

(i<1)
How to determine the approximate van't Hoff factor

In the following discussion, the solvent is


water. The general principles apply to all solvent,
but the details vary.
Some relevant definitions:
Electrolyte: This is a compound which forms
hydrated ions in solution. It resultant solution has
the property that it conducts electricity to some
extent.
Nonelectrolyte: This is a compound which does not
form hydrated ions in solution. It resultant solution
has the property that it conducts electricity about
as poorly as pure water..
Strong electrolyte: This electrolyte completely
(>98%) dissociates into the hydrated ions in
solution. It resultant solution has the property that
it conducts electricity very well.
Weak electrolyte: This electrolyte dissociates into
the hydrated ions in solution to only a limited
extent. It resultant solution has the property that it
conducts electricity poorly, but better than pure
water.
What is the van't Hoff factor:footnote1
The van't Hoff factor, symbol i, expresses how may
ions and particles are formed (on an average) in a
solution from one formula unit of solute.

Examples:

One formula unit of NaCl will create two


particles in solution, a Na+ ion and a Cl- ion.
One formula unit of CaCl2 will create three
particles in solution, a Ca+ ion and two Cl- ions.
One formula unit (molecule) of methanol CH3OH
will create only one particle in solution, since
methanol is a non electrolyte and does not
dissolve as ions.
One formula unit (molecule) of HF will form one
particle in solution, since it is a weak
electrolyte (weak acid).footnote2
One formula unit (molecule) of NH3 will form one
particle in solution, since it is a weak
electrolyte (weak base).footnote2

How to determine the approximate van't Hoff factor:


The first step is to be able to recognize whether one
is dealing with an electrolyte or a non electrolyte. It
is easier to recognize electrolytes, although the
student by this point should be able to recognize
the following organic functional groups which are
associated with non electrolytes (not a complete
list). The dashes, - and >, correspond to covalent
bonds to another atom, usually C.

The alcohol group -OH


The carboxylic acid group -COOH

The amine groups:


primary amine NH2, secondary amine >NH and ternary amine
>NThe ether group -O-

If you are not familiar with these groups, go back to


some of the CHEM 1100 handouts.
To recognize electrolytes:
All acids, bases and salts are electrolytes. The
definitions of these terms are found in CHEM 1110
handouts. This includes the salts and acids of the
polyatomic ions. Thus, you need to know your
polyatomic ion list which is in your lab manual or in
the CHEM 1110 handouts. You must also know this
list in order! Below is the some of the list in the
form of the acids. Notice the lines which delineate
the
8
acids
in
the
upper
right.
HClO HClO2
HBrO HBrO2
HIO HIO2
H2SO3
HNO2

HClO3 HClO4
HBrO3 HBrO4
HIO3 HIO4
H2SO4
HNO3

H3PO2 H3PO3 H3PO4


H2CO3

Strong acids: (belong to the class of strong


electrolytes)
The strong acids completely break up into
hydronium ions and the anions in solution. The
following are the strong acids:
The binary acids HCl, HBr and HI (the hydrohalic
acids except for HF). Thus, for example, HCl
dissolves in water by the reaction:
HCl (g) + H2O H3O+ + ClThis gives a van't Hoff factor or 2. (i = 2)
The 8 ternary acids in the upper right side of the
table above (to the right and above the blank nontabled boxes presented) are all strongfootnote3. Thus,
for example, HClO4 dissolves in water by the
reaction:
HClO4 + H2O H3O+ + ClO4This gives a van't Hoff factor or 2. (i = 2)
All other acids are weak, including the organic
acids which have the functional group -COOH.
Weak Acids:
electrolytes)

(belong to the class of weak

All weak acids have a van't Hoff factor of


approximately 1.

Example: The acid HClO2 has a van't Hoff factor of


1. This acid is, according to the table above, a weak
acid.
Example: The acid HF has a van't Hoff factor of
1. This binary acid is not HCl, HBr or HI and is
therefore a weak acid.
Example: The acid CH3COOH has a van't Hoff factor of
1. This acid is not a mineral acid, but rather an
organic acid. All organic acids, if they dissolve, are
weak acids in water solutions.
Strong Soluble Bases:
The strong soluble bases are the hydroxide
compounds of group I metals and group II metals
from Ca down on the periodic chart. All other metal
hydroxides are insoluble bases and only a very
small amount will dissolve in water. (Notice that OHwas on your polyatomic ion list!)
Examples:
LiOH has a van't Hoff factor of two. LiOH is a strong
soluble base (group 1 metal hydroxide) and
dissolves in water according to:
LiOH (s) Li+ + OHThus, each formula unit yields two ions total.

Ca(OH)2 has a van't Hoff factor of three. Ca(OH)2 is a


strong soluble base (group 1 metal hydroxide) and
dissolves in water according to:
Ca(OH)2 (s) Ca2+ + 2OHThus, each formula unit yields three ions total.
Insoluble Bases:
These are irrelevant since they are insoluble in
water. Examples include: Mg(OH)2, Fe(OH)3,
Zn(OH)2, etc.
Weak Soluble Bases:
Most weak soluble bases may be recognized by
being nitrogen compounds. These are either
amines (see above) or are nitrogen compounds
with nitrogen covalently bonded to hydrogen.
Examples:
ammonia
methyl
amine
hydrazine

NH3
CH3NH2
H2NNH2

Salts are Strong Electrolytes:footnote4


Salt break up into their ions. For binary salts break
into the individual metal ions (cations) and
nonmetal ions (anions)

Some typical examples of


binary salts:
i=
NaCl(s) Na+ + Cl2
i=
Li2S(s) 2Li+ + S23
i=
CaBr2(s) Ca2+ + 2Br3
3+
- i=
FeCl3(s) Fe + 3Cl
4
For salts with polyatomic ions (here's where you
need to know your polyatomic ions - learn them if
you haven't by now) break up into metal ion (cation)
and the polyatomic ion as a unit.
Some typical examples that
have polyatomic ions
Na2SO42i=
(s) 2Na+ + SO423
Fe3(PO4)2 (s) 3Fe2+ + 2
i=5
3PO4
Salts of weak bases. (Recall that the weak soluble
bases are the nitrogen compounds other than
HNO3 and HNO3.)
Some typical examples of salts
formed from weak bases:
NH4Cl (s) NH4+ + Cli=

2
CH3NH2NO3 (s) CH3NH3+ + i =
NO32
i=
(NH4)2SO4 (s) 2NH4+ + SO423
+
3- i =
(NH4)3PO4 (s) 3NH4 + PO4
4
Summary:
All water soluble compounds have a van't Hoff
factor of approximately 1 except:
Compounds which begin with metal ions. These
include
salts
and
strong
bases.
Soluble salts of weak bases (originating from
nitrogen compounds - review section on
recognizing
weak
bases.)
Strong acids - so you need to be able to recognize
a
strong
acid.
Strong soluble bases (redundant) - so you need to
be able to recognize a strong soluble base. Back
to top
Some more subtle caveats
Actual measurements of the vant Hoff factors often
yield values slightly different from that obtain by
the calculations so far described. These difference
could be due to several factors, but some of these
include:

Some momentary association for the anions and


cations in solutions. This phenomenon is
dependent upon concentration. For example, for
HCl the vant Hoff factor for a 0.001 M solution is 1.98,
and for a 0.20 M solution is 1.90. Thus, for these
solutions, the vant Hoff factor is slightly lower than
the expected 2.
However other effects might increase this
number. For example, for HCl at 1.00 M, the vant Hoff
factor is 2.12, that is higher than expected. The
following is a table of vant Hoff factors reprinted
from Fundamental Principles of Physical
Chemistry by Carl F. Prutton and Samuel H. Maron,
(revised, The MaMillan Company, NY 1951)
van't Hoff factors for some electrolytes
HNO NH4C CuSO H2SO CoCl K2SO K3Fe(CN)
Cm /M HCl
3
l
4
4
2
4
6
0.000
3.92
5
0.001 1.98
2.84 3.82
0.002 1.97
2.88
3.70
0.002
1.61 2.72
2.83
5
0.005 1.95 1.97 1.95 1.54 2.59 2.80 2.77 3.51
0.01 1.94 1.96 1.92 1.45 2.46 2.75 2.70 3.31
0.05 1.90 1.91 1.88 1.22 2.21 2.64 2.45 3.01

0.10
0.20
0.40
1.00
2.00
4.00

1.89 1.89 1.85 1.12 2.12 2.62 2.32 2.85


1.90 1.87 1.82 1.03 2.04 2.66 2.17 2.69
1.86
1.98 2.78 2.04
2.12 1.92 1.79 0.93 2.17 3.40
2.3
2.04 1.80
2.73 4.58
8
3.4
2.24 1.80
3.79
0

You should notice that some of the numbers are


higher and some are lower than the numbers
predicted from the simple treatment above. The
ones that are above, for example, H2SO4 may be
involved in other equilibria such as:

H2SO4 + H2O HSO4- + H3O+ since the first


protonic hydrogen is strong and
HSO4- + H2O SO42- + H3O+ since HSO4- is a weak
acid to the extent of approximately 1%.

These facts largely account for the factor that is


greater than the strong acid value of 2.
On the other hand, most salts have a van't Hoff factor
smaller than expected, and gets smaller as the
concentration goes up. It is thought that this is due
to the strong tendency for the cations (+) and
anions (-) to stay in close proximity and behave as if
they were chemically bound.

Solutions, however, can be quite complex,


expecially as the concentrations of the salts
approach saturation. For example, the case for
CoCl2 which approaches the expected 3 as the
concentration goes down, but also goes up at the
higher concentrations. (...and a minimum at about
0.1 M.) General rules under these conditions are not
readily available and each case must be
considered individually.

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