Apparent molar property

An apparent molar property of a solution component Apparent (molar) properties are not constants (even at a
in a mixture or solution is a quantity defined with the pur- given temperature), but are functions of the composition.
pose of isolating the contribution of each component to At infinite dilution, an apparent molar property and the
the non-ideality of the mixture. It shows the change in the corresponding partial molar property become equal.
corresponding solution property (for example, volume)
Some apparent molar properties that are commonly used
when all of that component is added to the solution, per are apparent molar enthalpy, apparent molar heat capac-
mole of component added. It is described as apparent
ity, and apparent molar volume.
because it appears to represent the molar property of that
component in solution, provided that the properties of the
other solution components are assumed to remain con-
stant during the addition. However this assumption is of- 1 Relation to molality
ten not justified, since the values of apparent molar prop-
erties of a component may be quite different from its mo- The apparent (molar) volume of a solute can be expressed
lar properties in the pure state. as a function of the molality b of that solute (and of the
For instance, the volume of a solution containing two densities of the solution and solvent). The volume of so-
components identified[1] as solvent and solute is given by lution per mole of solute is

( )
1 1
V = V0 + ϕ V1 = Ṽ0 n0 + ϕ Ṽ1 n1 + M1 .
ρ b
where V0 is the volume of the pure solvent before adding
the solute and Ṽ0 its molar volume (at the same temper- Subtracting the volume of pure solvent per mole of solute
ature and pressure as the solution), n0 is the number of gives the apparent molar volume:
moles of solvent, ϕ Ṽ1 is the apparent molar volume of
the solute, and n1 is the number of moles of the solute in ( )
the solution. 1 1 1 M1
ϕ
Ṽ1 = − 0 +
b ρ ρ 0 ρ
This equation serves as the definition of ϕ Ṽ1 . The first
term is equal to the volume of the same quantity of sol-
vent with no solute, and the second term is the change 2 Relation to partial (molar) quan-
of volume on addition of the solute. ϕ Ṽ1 may then be
considered as the molar volume of the solute if it is as- tities
sumed that the molar volume of the solvent is unchanged
by the addition of solute. However this assumption must The relation between partial molar properties and the ap-
often be considered unrealistic as shown in the Examples parent ones can be derived from the definition of the ap-
below, so that ϕ Ṽ1 is described only as an apparent value. parent quantities and of the molality.
An apparent molar quantity can be similarly defined for
the component identified as solvent ϕ Ṽ0 . Some authors
have reported apparent molar volumes of both compo- ¯ ∂ ϕ Ṽ1
[2][3] V1 = ϕ Ṽ1 + b .
nents of the same solution. ∂b
Apparent quantities can also be expressed using mass in-
stead of number of moles. This expression produces ap-
parent specific quantities, like the apparent specific vol-
3 Relation to activity coefficient of
ume. an electrolyte
The apparent molar volume of a dissolved electrolyte in a
V = V0 + ϕ V1 = v0 m0 + ϕ v1 m1 concentrated solution can be linked to the statistical com-
ponent of its activity coefficient:
where the specific quantities are denoted with small let-
br(r+h−ν)
ν ln(1 + 55.5 ) − ν ln(1 − 55.5 ) + 55.5(1+ 55.5
h−ν br h br
ters. lnγs = br
)

1
2 6 SEE ALSO
4 Examples
4.1 Electrolytes
The apparent molar volume of a salt is usually less than
the molar volume of the solid salt. For instance, solid
NaCl has a volume of 27 cm3 per mole, but the apparent
molar volume at low concentrations is only 16.6 cc/mole.
In fact, some aqueous electrolytes have negative apparent
molar volumes: NaOH −6.7, LiOH −6.0, and Na2 CO3
−6.7 cm3 /mole.[4] This means that their solutions in a
given amount of water have a smaller volume than the
same amount of pure water. (The effect is small how-
ever.) The physical reason is that nearby water molecules
are strongly attracted to the ions so that they occupy less
space.
4.2 Alcohol
Excess volume of a mixture of ethanol and water
Another example of the apparent molar volume of the as a difference between the volume of the mixture and
second component being less than its molar volume as a the volume of a binary submixture of a given composi-
pure substance is the case of ethanol in water. For ex- tion like:
ample, at 20 mass-percent ethanol, the solution has a vol- c Ṽ2 = V −V01
ume of 1.0326 litres per kg at 20 °C, while pure water
is 1.0018 L/kg (1.0018 cc/g).[5] The apparent volume of
the added ethanol is 1.0326 L - 0.8 kg x 1.0018 L/kg =
0.2317 L. The number of moles of ethanol is 0.2 kg /
(0.04607 kg/mol) = 4.341 mol, so that the apparent mo-
lar volume is 0.2317 L / 4.341 mol = 0.0532 L / mol =
53.2 cc/mole (1.16 cc/g). However pure ethanol has a
molar volume at this temperature of 58.4 cc/mole (1.27
cc/g). The nonideality of the solution is reflected by a
slight decrease (roughly 2.2%, 1.0326 rather than 1.055 6 See also
L/kg) in the volume of the combined system upon mix-
ing. As the percent ethanol goes up toward 100%, the
apparent molar volume rises to the molar volume of pure
ethanol.
4.3 Electrolyte - non-electrolyte systems
Apparent quantities can underline interactions in elec-
trolyte - non-electrolyte systems which show interactions
like salting in and salting out.
5 Multicomponent mixtures or so-
lutions
For multicomponent solutions, there definition of appar-
ent molar properties can be stated in several ways. For
the volume of a ternary (3-component) solution with one
solvent and two solutes as an example, there would still
be only one equation (V = Ṽ0 n0 + ϕ Ṽ1 n1 + ϕ Ṽ2 n2 ) ,
which is insufficient to determine the two apparent vol-
umes. (This is in contrast to partial molar properties,
which are intensive properties of the materials and there-
fore unambiguously defined in multicomponent systems.)
One description of ternary aqueous solutions considers
only the weighted mean apparent molar volume of the
solutes,[6] defined as ϕ Ṽ (n1 , n2 ) = ϕ Ṽ12 = nV1−V
+n2 ,
0
where V is the solution volume and V0 the volume of
pure water solvent.
Another method is to treat the ternary system as pseu-
dobinary and define the apparent molar volume of each
solute with reference to a binary system containing both
other components: water and the other solute.[7] The
apparent molar volumes of the two solutes are then
ϕ
Ṽ1 = V −V (solvent+solute
n1
2)
= V −(Vn01+V2 ) and ϕ Ṽ2 =
V −V (solvent+solute 1) V −(V0 +V1 )
n2 = n2
The apparent molar volume of two components or solutes
considered as one pseudocomponent ϕ Ṽ12 or ϕ Ṽij is not
to be confused with volume of a binary submixture Vᵢ of
the ternary mixture V or Vᵢ .
Of course the complement volume of a component in re-
spect to other components of the mixture can be defined
n2
There are situations when there is no rigorous way to de-
fine which is solvent and which is solute like in the case of
liquid mixtures (say water and ethanol) that can dissolve
or not a solid like sugar or salt. In these cases apparent
molar properties can and must be ascribed to all compo-
nents of the mixture.
• Volume fraction
• Ideal solution
 3

• Regular solution

• Enthalpy change of solution

• Solvation shell

• Partial molar property

• Excess molar quantity

• Thermodynamic activity

7 References
[1] This labelling is arbitrary. For mixtures of two liquids ei-
ther may be described as solvent. For mixtures of a liquid
and a solid, the liquid is usually identified as the solvent
and the solid as the solute, but the theory is still valid if
the labels are reversed.

[2] Rock, Peter A., Chemical Thermodynamics, MacMillan

1969, p.227-230 for water-ethanol mixtures.

[3] H. H. Ghazoyan and Sh. A. Markarian (2014)

DENSITIES, EXCESS MOLAR AND PARTIAL MO-
LAR VOLUMES FOR DIETHYLSULFOXIDE WITH
METHANOL OR ETHANOL BINARY SYSTEMS AT
TEMPERATURE RANGE 298.15 – 323.15 K PRO-
CEEDINGS OF THE YEREVAN STATE UNIVER-
SITY no.2, p.17-25. See Table 4.

[4] Herbert Harned and Benton Owen, The Physical Chem-

istry of Electrolytic Solutions, 1950, p. 253.

[5] Calculated from data in the CRC Handbook of Chemistry

and Physics, 49th edition.

[6] Citric acid Apelblat, Alexander (Springer 2014) p.50

ISBN 978-3-319-11233-6

[7] Citric acid Apelblat p.320

8 External links
• Apparent Molar Properties: Solutions: Background
• The (p,ρ,T) Properties and Apparent Molar Vol-
umes of ethanol solutions of LiI or ZnCl2
• Apparent molar volumes and apparent molar
heat capacities of Pr(NO3)3(aq), Gd(NO3)3(aq),
Ho(NO3)3(aq), and Y(NO3)3(aq) at T = (288.15,
298.15, 313.15, and 328.15) K and p = 0.1 MPa
• Isotopic effects for electrolytes apparent properties
4 9 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

9 Text and image sources, contributors, and licenses

9.1 Text
• Apparent molar property Source: https://en.wikipedia.org/wiki/Apparent_molar_property?oldid=742797968 Contributors: Eric
Kvaalen, SmackBot, Paxse, Sadads, Christian75, Dirac66, WilfriedC, SchreiberBike, Addbot, Lightbot, Yobot, Daniele Pugliesi, MagnInd,
ZéroBot, Hennui, BG19bot and Anonymous: 20

9.2 Images
• File:Excess_Volume_Mixture_of_Ethanol_and_Water.png Source: https://upload.wikimedia.org/wikipedia/commons/4/45/Excess_
Volume_Mixture_of_Ethanol_and_Water.png License: CC BY-SA 3.0 Contributors: de:Dortmunder Datenbank; en:Dortmund Data Bank
Original artist: Wilfried Cordes

9.3 Content license

• Creative Commons Attribution-Share Alike 3.0