Lebanon Valley College

Annville, Pennsylvania

The purpose of this paper on interaction

and the one to follow in the next issue is to present
experimental and theoretical information that can
serve as source material for people interested in developing an experiment involving the study of interaction. These papers will contain experimental data
obtained from an extensive laboratory investigation,
illustrat,ionsof dierent methods of data processing, and
considerations of the theoretical implications and
significance of the data. One of the features of these
presentations is the construction of a model for a chemical system and the testing of the model using the experimental data collected.
When two or more substances form a solution, the
degree of interaction between the components will
dcternline the extent to which the structure and bondiug
of the substances are altered. By studying the properties of a solution the type and degree of interaction
can he established. Some of the different types of
interaction are given in Table 1.
There are numerous experimental procedures that
can be used to investigate interaction in chemical
systems. Although the measurements of such properties as freezing point, boiling point, osmotic pressure,
and vapor pressure are made for the purpose of demonstrating the deviation of a property of a solution from
ideality, the data from these same types of st,udies
could be used to consider interactions if desired. In
the literature, frequent reference is made to the use of
qualitative arguments developing an interaction interpretation of data such as heat capacity, refractive
index, and dielectric constant. Quantitative considerations of interaction have been developed using
The investigation reported here constitutes in part some of the
laboratory work completed by a group of six high school teachers,
two college students, and four college professors who participated
in an eight-week conference at Lebanon Talley College during
the summer of 1963. This conference wa? conducted to design
and develop laboratory experiments and was held in conjunction
with the laboratory development program of the Chemical Bond
Aooroach
Proiect conducted under the aus~icesof the National
-.~r
Science Foundation. The work on interaction was continued
during the first semester of the 1963-64 academic year by the
authors of this paper and by the students enrolled in a sophomore
chemistry course a t Lebanon Valley College.
The suthors wish to express their appreciation to Barry B.
Barnhart, Paul C. Billett, David H. Deck, Harold F. Emmitt,
Robert S. Hamilton, James E. Livengood, William N. Stakely,
and Ronald S. Treiohler for collecting the majority of the primary
data used in this paper. The comments and suggestions given by
L. E. Strong were very useful in developing the section on the
interpretation of the data. Acknowledgment is also made to the
National Science Foundation for the financial support of aportion
of this work.
1 Present address:
I.ongwood College, Farmville, Virginia.
~

methanol-water system

such approaches as solubility determinations, thermochemical, electrometric, and activity measurements,

spectrophotometric and conductivity methods. Of a
more sophisticated nature are the studies of interaction
that have been conducted on the effects of substances
on the structure of liquids serving as solvents. Experimental methods used for such investigations include exchange reactions (4), X-ray diffraction studies
(6),Raman spectroscopy (6),and NMR methods (7).
Nature of the Investigation

The investigation of dipole-dipole interaction in the

methanol-water system was carried out by collecting
mass-volume and time-temperature data for the formation of a series of methanol-water solutions, each having
a different composition. An elementary approach to
analyzing the data obtained from such a study could
involve a consideration of density and temperature
change (AT), or heat transfer (Q), as a function of the
composition of the system. More useful information
about interaction in the system could he obtained by
finding the volume change (AV) and the enthalpy of
solution [A?I (solution)] as a function of composition.
Of even more significance would be a calculation of the
apparent molal volume (+V)and the apparent molal
enthalpy (+H).A more sophisticated approach
would involve finding the change in partial molal
volume (AP) and partial molal ent,halpy
With
sufficientdata, the enthalpy, entropy, and free energy
changes can he calculated.
The methanol-water system was investigated for
changes in properties as a function of mole fraction
using a continuous variation experimental design (8).
Seven different compositions were studied ranging from
85% (percent mass) methanol-15% water to 15%
methauol-85% water. For each composition, 14
sets of mass-volume and time-temperature data were
collected. These primary data were used to calculate
such secondary data as densities, apparent molal volumes, and enthalpies of solution. After applying a
statistical rejection procedure to the data, a given
property of the system was plotted against the conlposition of the system. Each graph was studied to
determine which type of interaction was indicated in
the syst,em.

(a).

Tnhle
Intermtion
. - ..1.
. . Tvaer
.,-.-of
.~
~~~- - ~ -

Type of interaction

Chemical system

Dipole-dipole
Ion-dipole
Ion-ion
Ion paim
Locslised hydrolysis

Methanol-ethanol
Potassium hydroxide-water
Mercury(I1) ion-iodide ion
LeFe(CN)swater
Potassium acetate-water

Reference

Volume 42, Number 6, June 7 965

(1)

(a

(8)

/ 309

Procedure

After the assigned masses of reagent grade anhydrous

methanol and distilled water were equilibrated in closed
containers in a constant temperature bath a t 25.00C,
the reagents were poured simultaneously into a 180-ml
tall-form beaker containing a thermometer graduated
in O.lC units. Time-temperature readings were
recorded every 30 sec for 10 min after mixing. The
beaker and contents were covered with aluminum foil
and placed in a constant temperature bath. When
the temperature of the reaction mixture reached
25.00C, the mass of a 25.00-ml sample of the mixture
was found. The masses of the reactants used in the
calculations were the masses transferred.
Using the primary data and the densities of the
reactants reported in the literature (9),the volumes
and masses of the reactants and the reaction mixtures
were found. The A V , +VH20,,,,
and +Vu.oHwere calculated (10). From time-temperature curves, AT for
the system was found by extrapolation (11). Using
the A T , the heat capacity of the reaction mixture reported in the literature ( I f ) , the experimentally determined calorimeter constant, and the mass of the
reaction mixture, Q and AH (solution) at 25.00C
were calculated for each composition of the system
studied. I n addition, the partial molal enthalpies of
solution were found (IS). The secondary data were
processed using the standard deviation method for
data rejection (14).
For a chemical system composed of two miscible
liquids, the AV or *V and A T , Q , or AH (solution) for
the system can be used to consider interaction. Three
major generalizations can be advanced for this purpose
and are summarized in Table 2.
Table 2.

Relationship of thermodynamic functions

Ideal

AV, AT, Q, and AH

Solvation

AV, Q, and AH <O

AT > 0
AV, AH, and Q > 0
AT < 0

Association

'Vt
'V,

VI
V,
%I'
< V,
'v, < V R
*V, > V ,
'V* > V ,
=
=

Mass-Volume Data

Volume change: For all compositions studied, a

negative volume change was found indicating that
the type of interaction is solvation. A graph of AV
against mole fraction of methanol, XaaeoH(Fig. 1)
indicates that the maximum interaction appears to
= 0.35.
occur a t X,.
Apparent molal volume: These data show that the
apparent molal volume of water is less than the molal
volume of water for all compositions studied. There
fore, the predominant type of interaction is solvation.
The plot of +VH,oagainst X,,,, (Fig. 2) indicates that
the maximum interaction occurs in the solutions that
have a large concentration of methanol while the plot
of 'VMsOE
against XM.OEshows that the maximum
interaction occurs a t XLI~OH
= 0.20 to 0.25. Although
the composition where maximum interaction appears to
occur is not the same for AV and for 'V,,,. and

AV versus mole fraction of methanol.

'VH,O,the difference might be expected.

AV is the
arithmetical mean of the differences between the apparent molal volumes of methanol and of water and
their respective molal volumes, weighted according t o
the number of moles of methanol and of water in the
solution. Therefore, AV represents the combined
contribution of the structural changes in water and in
methanol. The apparent molal volumes resolve AV
into its component parts: that due to the structural
changes associated with methanol and that associated
with water.

Generalizations on Interaction in a System of

Two Miscible Liquids

Type of
interaction

310

X~ma
Figure 1.

Journal of Chemical Educafion

Figure 2. Apparent molal volumes versus mole fraction of methonol

(0indicates per mole of woter and 0 indicates per mole of methanol.)

Thermochemical Data

Inspection of the data for AT and Q indicates that the

predominant type of interaction is solvation. However, there would be little value in plotting either property against mole fraction because neither function is
expressed in terms of moles. Enthalpies and partial
molal enthalpies of solution are more useful. From the
enthalpies, information about both the predominant
type of interaction and the degree of interaction is obtained.
Enthalpy of solution: The enthalpies of solution per
mole of methanol, per mole of water, and per mole of
solution are all negative for all compositions studied.
Solvation is the predominant type of non-ideal interaction. The AH (solution) per mole of solution is equal to
the arithmetic mean of the AH (solution) per mole of
water and the AH (solution) per mole of methanol,
weighted according to the mole fractions of the components. The plots of these enthalpies of solution
against XaeoHshow a region of maximum interaction a t
X u . 0 ~ = 0.25.

5 -0.6
0

.3 -0.4

?j-0.2
0

0.2

0.4
Xxmx

0.6

0.8

1.0

Figure 3. (a) Enthalpy of solution per mole of water and per mole of
methanol. (0indicates per mole of woter and 0 indicatsr per mole of
methanol.)

Rgure 3. (b) Enthdpy of solution per mole of solvtlon versus mole

frodion of methond

Partial molal enthalpy of solution: The partial molal

enthalpy of solution per mole of water was obtained by
plotting the AH (solution) per mole of methanol against
the mole ratio (nE,o/nar.o~). For a given mole ratio,
the slope of the curve is d(AH)/d(na,o). The partial
molal enthalpy of solution per mole of methanol was
obtained in a similar manner.
The partial molal enthalpies of water and of methanol
plotted against X H ~ O(Fig.
H 4) indicate that the predominant type of interaction is solvation.

should be able to develop a reasonable mechanism regardless of the rigidity with which the data are processed. If it is desirable to stress the idea of interaction, one approach that has proved to be very successful
is to have the students develop a model for the chemical
system based on a series of assumptions and to test the
model using the data collected.
The construction of models for water and for aqueous
solutions has been the subject of a number of papers.
Born (15) was one of the first individuals to advance a
model for a solution. Bernal and Fowler (16) advanced
the tetrahedral model for the structure of water. In
contrast to this model, Pauling (17) has suggested that
water is a clathrate-like structure involving dodecahedra arranged in random ways relative to each other.
The sphere-in-continuum model for an aqueous solution
has been proposed by Fuoss (18). Other models for
aqueous solutions have been advanced by Buckigham
(19), by Frank (80), and by Diamond (21).
Marchi and Eyring (22) have recently applied the significant structure theory to water. The model for
water that they propose shows reasonable agreement
with experimental data. Gurney (25),Davies (24), and
Hunt (65) have included in their presentations models
for the structure of water and of aqueous solutions.
A structural model for the methanol-water system can
be constructed on the basis of five assumptions. These
assumptions are:
(1) In water in the pure liquid state, a water molecule is tetrahedrally bonded to four other water molecules through hydrogen bridge bonding.
In Figure 5, the bondmg of a water molecule is shown
to occur a t the two positions on oxygen (Position 1 and
2 in Fig. 5) and through each of the two hydrogens
(Positions 3 and 4 in Fig. 5) giving a total of four bonding sites for each water molecule. The number of

Model Proposed and Tested

If one wishes to emphasbe solution formation, a very

useful approach is to have the students present a possible mechanism for the solution process a t the molecular
level based on their experimental data. The students

Figure 5.

Figure 4. PorHol mold enthalpies of soluHon versus mole frastlon of

methanol. (0indicahs the enthalpy changes per mole of water, end
0 Indicates the enthalpy changes per mole of methanol.)

bonding sites that will be occupied in a water molecule

will decrease with an increase in temperature. At
25"C, it is assumed that a majority of the bonding sites
of the water molecules are filled. Thus, the predominant structure in water is assumed to be tet,rahedral.
(2) In methanol in the pure liquid state, a methanol
molecule is bonded to two other methanol molecules
through hydrogen bridge bonding giving a chain structure. In Figure 6, the bonding of a methanol molecule
is shown to occur a t the one position on oxygen (Position
2 in Fig. 6) and through the hydrogen of the hydroxyl
group (Position 3 in Fig. 6). It is assumed that the
hydrogens of the methyl groups do not participate in
hydrogen bridge bonding. There is not enough hydroxyl hydrogen available in methanol to bond Position
1on the oxygen of the methanol molecule. Thus, only

iU
Hydrogen bridge bonding in woter in the pure liquid rtote.

Volume 42, Number 6, June

1965

31 1

two thirds of the honding sites on a methanol molecule

or two sites would be expected to be filled. The predominant stmcture in liquid methanol is assumed to he
a chain stmcture. The methanol molecules are unsaturated in terms of hydrogen bridge bonding having a t
least one hondmg site per methanol molecule unoccupied.
(3) The dipole moments of water and methanol
molecules are considered to be point charges and the
attraction between molecules is due to electrostatic
forces.
In liquid water, liquid methanol, and methanol-water
solutions, there would he dipole-dipole attractions hetween the molecules. This would imply that the waterwater bonds, the methanol-methanol bonds, and the
methanol-water bonds would each have characteristic
energies, EHK-a,o, EM.~H-M.oH,
and Emon-are.
(4) The addition of methanol to water or methanolwater systems of high mole fraction of water could result primarily in the suhstitution of methanol molecules
for water molecules in the water structure.
The water is saturated in terms of filled honding sites.
The substitution of methanol for water could occur a t
each of the four filled honding sites of each water molecule or a t Positions 1, 2, 3, and 4 in Figure 5. The
process could be represented by
H,O(H,O).

+ MeOH 2 HzO(H,O)~M~OH
+ H,O

(1)

The extent of substitution will depend on the mole fraction of methanol in the system.
(5) The addition of water to methanol or methanolwater systems of high mole fraction of methanol could
result in the substitution of water molecules for methanol molecules in the methanol structure. Also, addition of water molecules to the unoccupied sites of the
methanol molecules could occur.
The substitution of water for methanol could occur a t
each of the two filled bonding sites in a methanol molecule or a t Position 2 and 3 in Figure 6. This process is
represented by equation (2). At the same time, a water
MeOH(Me0H).

+ H20d M~OH(IM~OH)(H%O)
+ MeOH

(2)

molecule may add to the unoccupied bonding site on the

oxygen of a methanol nlolecule as represented by eqnation (3).
MeOH(MeOH)?

+ HaO e MeOH(MeOH)n(H*O)

(3)

The extent of suhstitution and of addition will depend

on the mole fraction of water in the system.
The usefulness of the model can he determined by
testing its validity in terms of the experimental data.
This procedure represents an attempt to use macroscopic data to test a model that provides a microscopic
view of the system.

Figure 6.

312

Hydrogen bridge bonding in methanol in the pure liquid stole.

Journal of Chemical Education

The testing of the validity of the model can be begun

by considering the effectof adding water to methanol on
the volume of water and of methanol. From Figure 2,
the *VHL0decreases rapidly as X M ~ Oincreases
H
until
Xaaeoa = 0.6. On the other hand, the *VM.OHdecreases rapidly as XMeoHdecreases until XMeoH= 0.25.
After this point, *Vx.oH increases. At mole fractious
above 0.6, the 'VH~Ocontinues to decrease but a t a
slower rate. These data suggest that the addition of a
small quantity of methanol to water alters the structure
of the methanol appreciably with the predominant
structure of the solution being that of water. The
methanol molecules would be present in the solution in a
new configuration involving water molecules rather than
in the form of chains. At the same time, a small portion of the water structure will be altered by the interaction of methanol and water molecules. Thus, the addition of methanol to water has disrupted both the water
structure and the methanol structure as they would
exist in the pure liquid state. Under such conditions, a
methanol molecule is probably solvated with water
molecules so that the three bonding sites in a methanol
molecule (Positions 1, 2, and 3 in Fig. 6) might be filled
with water molecules. When the quantity of methanol
added to water is increased, there would be a decreasing
quantity of water available to solvate the methanol
molecules. This process would continue to destroy the
water structure giving rise to a new confignration.
When a large quantity of methanol is added, a point is
reached a t which the number of water molecules is
insufficient to occupy all of the bonding sites in methanol so that the solution now contains the methanolwater configuration as well as the chain structure of
methanol. From these considerations, it would appear
as if the mass-volume data are reasonably consistent
with the proposed model.
Next, consider the compatibility of the model and the
thermochemical data. The model is tested on the basis
of two processes as shown in equations (4) and (5).
Water or methanol is added to a methanol-water solution of sufficient quantity that the composition of the
solution does not change. The change in partial molal
enthalpy for equation (4) is equal to the enthalpy of a
mole of water in a methanol-water solution minus the
enthalpy of a mole of water in the pure liquid state.

When water is added to a methanol-water solution,

the model suggests that some or all four of the water
molecules on the four bonding sites of a water molecule
could be displaced by methanol molecules. According
to Assumption (4), the number of methanol molecules
bonded to water will be proportional to XM,OH. For
compositions where XM.OHis low, it would be expected
that not all of the water molecules will be substituted by
methanol molecules a t the hydrogen bonding sites on a
water molecule. When Xmeonis large, the majority of
the water molecules being added should be solvated by
methanol. If this description based on the model of the
effectof adding water to methanol is correct, the experimental partial molal enthalpy change for water should
be in agreement with that calculated from the bond
energies for the components of the system.

2. The composition of the system nhere there is maximum

interaction is at a mole ratio of three water molecules to one
methanol molecule.
3. The addition of methanol to water appears to cause a
collapse of hoth the water and the methanol structures resulting
in the formslcion of a new structure of lower enthalpy.
4. The solvation of methanol with water a t small Xwma
involves the addition of water a t the unsaturated bonding site of
methanol as well as substitution of water molecules for methanol
molecules. At large X m m , the primary process is suhstitution
with little if any addition occurring.
5. The addition of water to methanol appears to cause a
When the partial molal enthalpies of solution of water
collapse of both the water and the methanol structures resulting
are plotted against X M ~ Othe
A ,resulting curve as shown
in the formation of a new structure of lower enthdpy.
6. The solvation of water with methanol at all Xn.on inin Figure 4 is a straight lme and the slope ~ A L T / ~ X M ~ ~ E
volves predominantly the substitution of water molecules by
is a constant. Because the slope is constant the bondmethanol molecules at the bonding sites on a water molecule.
ing of methanol molecules with the water is occurring in
7. The strength of the water-methanol bonds is greater than
s regular fashion. Thus, the data support the assumpthat resulting from the asso&tian of water molecules or from
the association of methanol molecules. The methanol-methanol
tions on which equation (7) was developed, and the
bonds are stronger than the water-water bonds.
partial molal enthalpy changes per mole of water sup-

The change in the partial molal enthalpy of water

(AR) in terms of bond formation and bond rnpture
when water is added to a methanol-water solution of
X M ~isHgiven by equations (6) and (7) which were
developed from the assumptions.

port the proposed model.

When methanol is added to methanol-water solutions,
either substitution (eq. 2) or addition (eq. 3) can occur.
If addition occurs, the enthalpy change will be much
larger than if a substitution process is involved. The
slope of the curve in Figure 4 indicates that as Xn20increases the partial molal enthalpy of methanol increases
with a marked increase in the rate of change. These
data suggest that when methanol is added to methanolwater solutions of large XM.~H
substitution is the predominant process occurring. When methanol is added
to methanol-water solutions of large XHIO
hoth addition
and substitution occur.
The strength of the bonds in the methanol-water
system can be compared to the strength of the bonds in
methanol and in water. The basis for this comparison
is the change in partial molal enthalpies of solutions
based on the processes given in equations (4) and (5).
Because enthalpy change is a measure of bond energy,
the AFZ for equation (4) is a measure of the difference
between the bond energies per mole of water in a methanol-water solution of a given composition and the bond
energies per mole of water in the pure liquid state. The
AR for equation (5) may he viewed in an analogous
manner in terms of methanol.
From the plot of the change in the partial molal
enthalpies, the sign of the slopes of the curves in Figure
4 indicates that the methanol-water bonds are stronger
than the water-water or the methanol-methanol bonds.
In addition, the methanol-methanol honds are stronger
than the water-water honds since the slope (-bBH20/
~XM.OH)
for water isgreater than the slope (+dflM,oH/
~ X M . ~ for
H ) methanol in excess methanol where water
appears to interact with methanol mainly by suhstitution (eq. 2). These data tend to support the proposed
model. This interpretation of the data is only valid if
there are no new types of bonds formed in the solution
such as a water-methyl group bond. Although Benjamin and Benson(26) have reported the same relative
bond strengths as these data support, they raise a
question as to the possibility of bonding between a
methyl group of methanol and water molecules.
On the basis of the information obtained from this
investigation, the following statements might he made
about the interaction in the methanol-water system.
1. There is non-ideal interaction in the methanol-water
system, and the interaction invdves predominantly solvation.

Other features of the methanol-water systen~can he

developed from the proposed model, but the considerations presented should illustrate the use of a strnctural
model in conjunction with this type of laboratory investigation. The interpretation of the data requires
the students to relate volume and enthalpy changes to
hydrogen bonding, solvation, and interaction. The
model might be considered to he naive and an oversimplification of salvation compared to cont,emporary
theories of interaction in solution. However, the Droposed model does provide a means of interpreting the
data collected for the methanol-water system, and affords an opportunity to consider hydrogen bridge bonding, structure, and interaction in a more quantitative
fashion than is usually. done.
References
(1) BJEBRUM,N., Z. Ano~g.Allgem. Chm., 109, 275 (1920).
(2) BJERRUM,
N., KgL Danske. V i Dmkab., 7, No. 9 (1926):

"Selected Papers,"

Einar Munksgaard, Copenhagen,

1948.
(3) ROBINSON,
R. A., AND HARNED,
H. .4., Chm. Rev., 28, 419
(1941).
(4) BALDWIN,
H. A., AND TAUBE,H., J. Chem. Phys., 33, 206
(1960).
(5) BRADY,G. W., AND ROMANOW,
W. J., J . Chm. Phys., 32,
306 (1960).
G. E., J. Chm. Phys., 36, 90 (1962).
(6) WALRAFEN,
(7) MEIBOOM,
S., J. Chm. Phys., 34, 375 (1961).
(8) JOB,P., Ann. Chem., 9, 113 (1928).
(9) TIMMERMANS,
J., "The Physico-chemical Constants of

Binary Systems in Concentrated Solutions," Interscience

Publishers, Inc., New York, 1960, Vol. 4, p. 161.
(10) PITZER,K. S., AND BREWER,L., "Themodymmies," 2nd
ed., McGraw-Hill Book Company, Inc., 1961, p. 205.
(11) SHOEMAKER.
D. P.. AND GARLAND.
C. W.. "Emeriments in
Physical 'chemistry," Mc~rak- ill ' ~ o o dCompany.
Inc., New York, 1962, p. 111.
TIMMERMANS,J., "The Physicc-chemical Constants of
Binary Systems in Concentrated Solutions," Interscience
Publishers, Inc., New York, 1960, Yal. 4, p. 169.
PITZER, K. S., AND BREWER,L., "Thermodynamics,"
Znded., McGraw-HillBook Company, Inc., 1961, p. 384.
PA-TT,
L. G., "Probability and Experimental Errors in
Science," John Wiley and Sons, Ine., New York, 1961,
p. 88.
BORN,M., Physik. Z.,1, 45 (1920).
BERNAL,J. D., AND FOWLER,
R. H., J . Chm. Phys., 1,515
(1933).

PAULING,L., "Nature of the Chemical Bond," 3rd ed.,

Comell University Press, Ithaca, New York, 1960, p. 464.
SADEK,H., AND FUOSS,
R. M., J . Am. Chm. Soe., 72, 301
(1950).

Volume 42, Number 6, June 7 965

313

(19) BUCKINGHAM,
A. D., Discxis8ion Faraduy Soe., No. 24.151
(1957).
(20) FUNK. H. S., A N D WEN, W. Y., DibmSim Faraday Sot,,
No. 24, 133 (1957).
(21) DIAMOND,
R. M., J . Phys. C h m . , 67, 2513 (1963).
(22) MAECHI,R. P., AND EYRING,
H., J. Phy8. chem., 68, 221
(1964).

314

Journol of Chemical Education

(23) GURNEY,
R. W., "Ionic Processes in Solution," McGrswHill Book Company, Inc., New York, 1953.
(24) D ~ v m s ,C. W., "Ion Association," Butterworths, London,
1962, Chap. 14.
(25) HUNT, J. ,P., "Metal Ions in Aqueous Solution," W. A.
Benjarnm, Inc., 1963, Chap. 3.
(26) BENJAMIN,
L.,AND BENSON,G. C., J. Phy8. Chem., 67, 858
(1963).