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INTERNATIONAL SCHOOL OF STAVANGER

Chemistry Extended Essay


An Investigation into Volumetric Behaviour of
Salts and Saccharides in Aqueous Solutions

Candidate Name: Alexander Zakharov

Candidate Number: 000862-042

Word Count: 3963 words


Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Table of Contents
Content Page
Cover Page............................................................................................................ 0

Table of Contents................................................................................................. 1

List of Tables......................................................................................................... 2

Abstract................................................................................................................ 3

1. Introduction...................................................................................................... 4

2. Methodology for Data Collection..................................................................... 8

3. Primary Data Collected from the Laboratory Experiment.............................. 11

4. Processed Results........................................................................................... 12

5. Analysis of Volumetric Behaviour of Salts in Aqueous Solution..................... 16

5.1 More Efficient Packing of Ions...................................................................... 16

5.2 Ionic Radii..................................................................................................... 19

5.3 Distraction of Liquid Water Structure Due to Solvation............................... 20

6. Analysis of Volumetric Behaviour of Saccharides in Aqueous Solution.......... 24

7. Conclusion...................................................................................................... 26

7.1 Further Questions......................................................................................... 27

8. Bibliography.................................................................................................... 28

9. Appendices (1-7)....................................................................................... 29-36

Page 1
Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
List of Tables
Table Page
Table 1: Variables and Method of Controlling...................................................... 9

Table 2: List of Apparatus..................................................................................... 9

Table 3: Laboratory Data for Sodium Chloride................................................... 11

Table 4: Laboratory Data for Potassium Chloride.............................................. 11

Table 5: Laboratory Data for Glucose (C6H12O6)................................................. 11

Table 6: Laboratory Data for Sucrose (C12H22O11)............................................... 11

Table 7: Density of an Aqueous Solution at Certain Concentration of Solute ….12

Table 8: Generating Values for Density of a Solution and Calculating Apparent

Molar Volume……………………………………………………………………………………………….. 13

Table 9: Change in Molar Volumes for the Chosen Salts and Saccharides......... 15

Table 10: Calculating Packing Efficiency of Sodium Chloride............................. 17

Table 11: Calculating Packing Efficiency of Potassium Chloride......................... 17

Table 12: Effect of Rearrangement into More Efficient Packing........................ 18

Table 13: Volumes of Anions and Cations in Aqueous Solution......................... 19

Table 14: Number of H2O Molecules that Need to Be Orientated..................... 22

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Abstract

The study was aimed at investigating the magnitude of deviation of salts and saccharides
from volume additivity by looking at the volume shrinkages of compounds that were
dissolved in water. Three processes were considered, which could potentially contribute to
the observed volume shrinkages. The research question of this study was the following:

How and why do the apparent molar volumes of salts and saccharides in aqueous
solutions differ from their molar volumes in a crystalline state?

In order to proceed with the investigation, it was necessary to collect experimental data. The
experimental data included masses of a fixed volume of different aqueous solutions, which
were then converted to densities using the formula:

After that, various analytical and graphical methods were used to calculate the shrinkages in
molar volumes of the chosen compounds.

The results showed that the volumes of the two salts (sodium and potassium chlorides)
undergo a significant shrinkage in comparison with the two sugars (glucose and sucrose),
volumes of which stay more or less constant.

Sodium chloride showed a more pronounced tendency to shrink in volume than potassium
chloride did. To explain the volume shrinkage of potassium chloride, it was enough to
assume that upon dissolution, the ions are rearranged into a more efficient packing.
However, such rearrangement was not sufficient to explain the volume shrinkage of sodium
chloride. In addition to their closer-packing, sodium ions orientate water molecules towards
themselves, causing local distraction of water structure. Change of ion sizes is not believed
to be a significant contributing factor.

The picture was quite different for the sugars, since they only underwent very slight
deviation from volume additivity. This is due to homogenous intermolecular interactions
between sugars and water molecules. However, it was observed that the volume of sucrose
shrank slightly more than the volume of glucose.

Word count: 300 words

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
1. Introduction

Water is the most abundant chemical compound on the surface of Earth, which covers

nearly 71% of the surface of our globe [6]. It is the key ingredient to most life on our planet.

Water became the environment, where the first simple forms of life appeared approximately

700 million years ago [7]. Even those, more developed forms of life that left the ocean and

settled on land, still predominantly consist of water. For instance, water makes up around

60% of human body mass [5]. Obviously, humans need access to fresh water, because it is

the key to survival [4]. It is not surprising that most of the human settlements developed

around the sources of fresh water.

In nature, water rarely exists as a pure substance. Perhaps, pure water can only be found in

laboratories, where it is distilled for scientific experiments. Since water is an excellent

solvent, most of the water is found in a form of aqueous solutions, including water in oceans

and in bodies of living organisms. In addition to that, it is reasonable to assume that most

biochemical processes take place in aqueous solutions since all the important biological

systems, such as cytoplasm, blood, lymph, saliva, urine, and sweat are aqueous solutions of

salts, proteins, carbohydrates, and lipids [2, 4]. The examples of such biochemical processes

are digestion of food and transportation of metabolites.

Understanding the properties of aqueous solutions and their behaviour is important to

various fields of knowledge and industries such as biochemistry, medicine and

pharmaceutical industry, agriculture and food processing, marine ecology, and water

purification.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042

While solutions can be considered a relatively basic topic in chemistry, it is still a subject for

numerous scientific studies and publications. Surprisingly, some elements of knowledge

about aqueous solutions that were thought to be understood for quite a long time can

become a subject for revision due to the development of modern analytical techniques. For

instance, progress in neutron and X-ray diffraction techniques has produced a very different

picture of ions in water [2].

The topic that is being investigated in the extended essay is volumetric behaviour of salts

and saccharides in aqueous solutions. This topic is interesting to investigate because there

are cases where volumetric behaviour of certain compounds is inconsistent with the

expectations. For instance, when sodium chloride is dissolved in water, the expected volume

increase of a solution does not match the actual volume increase of a solution. This

abnormal behaviour contradicts our common sense, which tells us that volume should not

change. This is why it is fascinating to find flaws in our logic and find the reasons for such

unexpected “tricks” of nature. Moreover, the topic is not frozen, i.e. the consensus about

volumetric behaviour of chemical compounds in aqueous solutions is not reached. This can

be supported by the fact that there are many ongoing studies and researches in this area of

chemistry. Surprisingly, different sources suggest their own data and theories. Especially, the

greatest contrast is seen between old and recent research publications.

The chosen area of study, i.e. volumetric behaviour of salts and saccharides in aqueous

solutions is quite a broad topic, which consists of numerous subtopics. Therefore, the

research was narrowed down to a specific question of study:

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042

How and why do the apparent molar volumes of salts and saccharides in aqueous

solutions differ from their molar volumes in a crystalline state?

This question undermines a comparison between molar volumes of crystal lattices and

aqueous solutions of several soluble chemical compounds, namely salts and saccharides, as

well as explaining the processes that cause the changes in molar volumes between the two

states.

In most cases, modern science uses very complex and technologically advanced analytical

techniques such as NMR, infrared spectroscopy, neutron and X-ray diffraction. Since many

schools do not possess such advanced equipment, it was decided to use simpler equipment,

which was available in a school laboratory. It was particularly interesting to see how

relatively simple macroscopic measurements of mass, volume and density of aqueous

solutions at different solute concentrations provided an insight into the behaviour of the

investigated compounds on a microscopic (molecular/ionic) level.

For this particular investigation, two different types of solutes were chosen. Two of them

were ionic salts (sodium chloride and potassium chloride), and the other two were sugars

(glucose and sucrose). The two sugars being studied are simple molecular compounds, while

the two chosen salts are made out of ions, i.e. giant ionic lattice structures. Nevertheless, all

the selected compounds will readily dissolve in water, which would enable a comparison to

be made between them.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
The results of laboratory experiments confirmed that the volumetric behaviour of salts and

saccharides in aqueous solutions is very different. To be more specific, the molar volumes in

the two states (crystal lattice and aqueous solution) of the chosen salts are different. There

was a distinct change in molar volumes between the crystalline and aqueous states. In the

case of sugars, the molar volumes were approximately the same before and after

dissolution.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
2. Methodology for Data Collection

Since the intention of this research was to investigate the change in molar volumes of salts

and saccharides during the transition from a crystalline to an aqueous state, I had to make

my own procedure (see page 10), which would allow the collection of relevant data. The

data should help me find the apparent molar volume of a solute, dissolved in water, at

infinite dilution. In order to do so, it was necessary to investigate densities of solutions at

different concentrations of solutes.

By knowing densities, it is possible to process them, using both graphical and analytical

methods, to determine the apparent molar volumes of the four compounds chosen for this

investigation. Refer to Section 4 (Processed Results) and Appendix 2 for more information

about the method for calculating apparent molar volumes of compounds at infinite dilution.

There are two ways to measure the density of a solution, direct and indirect. The direct

measurement can be done using an areometer. The density of a solution is directly

proportional to the buoyancy of an areometer. However, the accuracy of such density

measurement is not high enough, which is why using an indirect way of measuring the

density of a solution was employed. It involved measuring the mass and volume of a solution

and calculating its density using:

The density of a solution was calculated from the measured mass of a 10 cm3 sample of a

solution. The independent variable in the investigation was the concentration (mass) of a

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
solute and the dependent variable was the mass of a 10 cm3 sample of a solution. Many

controlled variables had to be accounted for, because any change could potentially affect

the accuracy of results.

A correct choice of apparatus was important. This is why a volumetric glass pipette was

chosen as well as a very accurate balance. This equipment allowed the collection of accurate

and relevant data for the investigation.

Table 1: Variables and Method of Controlling


Variable
Variable Method of controlling
type
Concentration of solute Use very accurate measuring scales to measure out the
Independent
(mass) mass of a solute.
Mass of a 10 cm3 sample Use very accurate balance and a volumetric glass
Dependent
of a solution pipette, which has a 10 cm3 mark.
Conduct the experiment at room temperature in the
Temperature
same laboratory ( 22,5 C).
Pressure Conduct the experiment in the same laboratory.
Amount of water Always measure out 100 cm3 of a water.
Controlled Use the purest chemicals that are available in the
Purity of chemicals
school laboratory.
Purity of water Use distilled water.
Measure out 10 cm3 of a sample of a solution using a
Volume of a sample
volumetric glass pipette.

Table 2: List of Apparatus

 Measuring cylinder, cm3


 Balance, g
 Volumetric glass pipette, cm3
 Several beakers
 Spatula
 Chemicals: glucose, sucrose, sodium
chloride and potassium chloride.
 Distilled water
 Thermometer

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Procedure:

1. The necessary equipment was gathered.

2. The preliminary experiment was conducted. See Appendix 1.

3. Six masses of each solute were measured out very accurately.

 The masses were 5g, 10g, 15g, 20g, 25g, and 30g.

4. Seven beakers were filled with 100 cm3 of distilled water.

5. Each mass was added to a separate beaker with water. The solution was stirred until

there were no visible crystals.

6. One of the beakers had no solute added to it, because it was a control beaker. The

control beaker filled with pure water was used to calculate the density of pure water.

7. A 10 cm3 sample of a solution was extracted from all seven beakers using a

volumetric glass pipette.

8. The mass of the 10 cm3 sample of a solution was measured using a balance.

9. The measurements of mass were repeated. In total, five measurements were made

for each concentration of a solute.

10. All the mass measurements were average and the density of a solution was

calculated using the formula: .

11. The steps above were repeated for the three remaining compounds.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
3. Primary Data Collected from the Laboratory Experiment

Table 3: Laboratory Data for Sodium Chloride


Mass of NaCl (g) 0,001 g Average Mass of Solution (g) Average Density of a Solution(g/cm3)
0,000 9,979 0,998
5,022 10,284 1,028
10,015 10,617 1,062
15,002 10,916 1,092
20,000 11,206 1,121
25,001 11,477 1,148
29,999 11,736 1,174

Table 4: Laboratory Data for Potassium Chloride


Mass of KCl (g) 0,001 g Average Mass of Solution (g) Average Density of a Solution (g/cm3)
0,000 9,979 0,998
5,004 10,293 1,029
9,999 10,588 1,059
14,998 10,871 1,087
20,000 11,125 1,113
24,998 11,385 1,139
29,999 11,615 1,161

Table 5: Laboratory Data for Glucose (C6H12O6)


Average Density of a Solution
Mass of Glucose (g) 0,001 g Average Mass of Solution (g)
(g/cm3)
0,000 9,979 0,998
5,005 10,168 1,017
9,998 10,325 1,033
14,995 10,465 1,047
19,999 10,605 1,061
24,997 10,737 1,074
29,999 10,864 1,086

Table 6: Laboratory Data for Sucrose (C12H22O11)


Average Density of a Solution
Mass of Sucrose (g) 0,001 g Average Mass of Solution (g)
(g/cm3)
0,000 9,979 0,998
5,002 10,189 1,019
10,001 10,365 1,037
14,998 10,532 1,053
19,999 10,670 1,067
24,999 10,838 1,084
29,999 10,970 1,097

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
4. Processed Results

In order to calculate the apparent molar volume of sodium chloride at infinite dilution, it was

necessary to find a function, which describes the relationship between the mass percentage

of sodium chloride in solution and the density of a solution.

Table 7: Density of an Aqueous Solution at Certain Concentration of Solute


%W(NaCl) (%) Average Density (g/cm3)
0,000 0,998
4,791 1,028
9,121 1,062
13,069 1,092
16,696 1,121
20,034 1,148
23,114 1,174

Relationship between the Mass Percentage of NaCl in


Solution and the Density of a Solution

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
When such curve (see previous page) was obtained, it became possible to use the equation

of a function to figure out the density of an aqueous sodium chloride solution at desired

concentrations, by plugging values of concentration into the equation.

The formula presented in Appendix 2 was used to calculate the apparent molar volume of

sodium chloride in aqueous solution. The assumption was that the density of water

remained constant, because the density of water would not be affected at infinite dilution.

Table 8: Generating Values for Density of a Solution and


Calculating Apparent Molar Volume
%W(NaCl) NaCl Density Volume of 100g Volume of Water Apparent Molar Volume
(%) (g/cm3) Solution (cm3) (cm3) (cm3/mol)
0,000 0,998 100,210 100,210 #DIV/0!
1,000 1,005 99,545 99,208 19,657
2,000 1,011 98,879 98,206 19,663
3,000 1,018 98,214 97,204 19,671
4,000 1,025 97,549 96,202 19,683
5,000 1,032 96,885 95,200 19,698
6,000 1,039 96,222 94,198 19,717

Now that the values for mass concentration of NaCl and the apparent molar volume of NaCl

in solution are known, it is possible to make a curve fit and determine the apparent molar

volume of a compound at infinite dilution by looking at the y-intercept of the plotted curve.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Finding the Apparent Molar Volume of NaCl at Infinite Dilution

The graph above demonstrates the method and uses all the measured data. However, for

the actual data, some anomalous points were filtered out at the stage of data quality

control. The table on the next page shows the apparent molar volumes, calculated using the

filtered data.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Table 9: Change in Molar Volumes for the Chosen Salts and Saccharides

Solute Apparent Molar


Molar Volume in
Type of Volume of Solute at Shrinkage
Chemical Crystalline State
Solute Name Infinite Dilution (%)
Formula (cm3/mol)
(cm3/mol)
Sodium
NaCl 27,0 18,6 31 %
Chloride
Salts
Potassium
KCl 37,6 26,7 29 %
Chloride
Glucose C6H12O6 116,7 114,8 2%
Saccharides
Sucrose C12H22O11 215,7 203,0 6%

It is evident from the results that significant volume shrinkage occurs when salts are

dissolved in water. The apparent molar volumes of both salts in aqueous solutions are

significantly lower that their molar volumes in a crystalline state. Apparently, sodium

chloride demonstrates a more pronounced tendency for volume shrinkage at dissolution

than potassium chloride.

In contrast to the salts, the apparent molar volumes of saccharides in aqueous solution do

not significantly differ from their molar volumes in a crystalline state. The volumes of these

saccharides remain almost unchanged upon dissolution in water. However, there is a slight

difference between the volume shrinkages of the two sugars.

All the values in the table were calculated using a method presented in Appendices 2 and 5.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
5. Analysis of Volumetric Behaviour of Salts in Aqueous Solution

The root cause for the volume shrinkage is assumed to be the contrasting forces of

interaction between the ions and their nearest neighbours in an ionic lattice and in an

aqueous solution. In an ionic lattice, each ion is surrounded by six oppositely charged ions,

where opposite charges and relatively strong electrostatic forces between them define the

structure of an ionic compound and the strength of interactions between ions. However, in

an aqueous solution, the ions are surrounded by water molecules. The binary ion-dipole

interactions between ions and water molecules are weaker than the ionic bonds in a lattice.

The contrast in interactions can lead to an increase in packing density during the transition

of ions from solid to aqueous phase, decrease in ionic radii, or distraction of liquid water

structure due to solvation. All of those processes can potentially contribute to volume

shrinkage of the salts.

The following part of the analysis will evaluate the potential degree of contribution of each

of the processes mentioned above.

5.1 More Efficient Packing of Ions

In order to analyse the packing density of the ions, it is necessary to refer to the literature

data about structures of ionic lattices and ionic radii. According to the literature, the overall

structure of both salts consists of two interpenetrating face-centred cubic arrays, one of

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
sodium or potassium ions and one of chloride ions [10]. The packing efficiency of such

structure depends on the relative dimensions of cations and anions.

For the known Na+, K+ and Cl- ionic radii, a simple calculation (see Appendix 4) results in

packing efficiency of 65% for solid NaCl and 55% for solid KCl.

Table 10: Calculating Packing Efficiency of Sodium Chloride


Radius of Radius of Sum of Lattice Unit cell Total volume of % of the volume in unit cell
a cation an anion radii constant volume 8 spherical ions of crystal occupied by
(pm) (pm) (pm) (pm) (m3) (m3) spherical ions
102 181 283 566 1,81E-28 1,171E-28 65 %

Table 11: Calculating Packing Efficiency of Potassium Chloride


Radius of Radius of Sum of Lattice Unit cell Total volume of % of the volume in unit cell
a cation an anion radii constant volume 8 spherical ions of crystal occupied by
(pm) (pm) (pm) (pm) (m3) (m3) spherical ions
138 181 319 638 2,60E-28 1,43E-28 55 %

With such relatively low packing efficiency in salt crystals, it is reasonable to assume a more

efficient packing of particles in aqueous sodium and potassium chloride solutions, because

when ions are dissolved in water, the electrostatic interactions between the ions are no

longer prevalent. In addition to that, water has a structure with numerous cavities, which

can be partially filled with ions.

Indeed, for potassium chloride, the observed change in molar volume can be fully explained

by rearrangement of ions in aqueous solution into more efficient packing (such as hexagonal

close-packed structure with 74% occupancy). Such packing would not be a surprise, since the

sizes of all three particles (K+, Cl-, and H2O are relatively close in size [9, 11]). The calculation

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
of apparent molar volume changes resulting from more efficient packing of ions in aqueous

phase is presented below.

Table 12: Effect of Rearrangement into More Efficient Packing

% of volume in unit % of volume in unit


Measured Apparent
cell of crystal Molar volume in cell of solution to be
Molar volume in
occupied by crystal (cm3/mol) occupied by
solution (cm3/mol)
spherical ions (%) spherical ions (%)

NaCl 65 % 26,99 18,64 94 %


KCl 55 % 37,58 26,66 78 %

The results in the table above show that the packing efficiency of potassium chloride goes

from 55% in ionic lattice to 78% in aqueous solution. This suggests that there is a more

compact packing of ions in water and that it is possible that the ions and water molecules

are arranged to a structure similar to the hexagonal close-packed. This process is sufficient

to explain the observed volume change for potassium chloride.

However, structural rearrangement and compaction of ions of sodium chloride would not be

sufficient to explain the observed volume changes, because the 94% packing efficiency does

not seem to be realistic. In other words, such more pronounced volume change of sodium

chloride cannot be solely explained by the rearrangement of ions. Therefore, two other

processes listed above (decrease in ionic radii or distraction of liquid water structure due to

solvation) should also be explored.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
5.2 Ionic Radii

At infinite dilution, the observed difference in apparent molar volumes of sodium and

potassium chlorides appeared to be approximately 8 cm3/mol (see above). All this difference

can be attributed to molar volumes of cations (Na+ and K+). Indeed, at infinite dilution, the

volumes occupied by bulk water and chloride ions are not expected to be affected when

sodium ions are substituted by potassium ions. That is because the distances between the

anions and the cations are large enough to prevent any kind of ion-ion interaction to occur.

The calculation presented in Appendix 6 is an attempt to explain the observed 8 cm3/mol

difference between sodium and potassium apparent molar volumes in infinitely diluted

aqueous solutions. It is assumed that the potassium and chloride ions remain constant in

size. The question is, how much smaller in size should the sodium ion be in aqueous solution

compared to the same ion in crystal lattice in order to explain the observed difference in

apparent molar volumes of sodium and potassium ions in aqueous solution?

Table 13: Volumes of Anions and Cations in Aqueous Solution

Measured Apparent Molar Apparent molar volume of Molar volume of Cl- in


volume in solution (cm3/mol) cation in solution (cm3/mol) solution (cm3/mol)

NaCl 18,64 0,17 18,47


KCl 26,66 8,19 18,47

The calculation in Appendix 6 shows that the radius of the sodium ions in aqueous solution

should barely exceed zero in order to explain the observed apparent molar volume

difference. It should become even smaller, if we assume some reduction in the potassium

ion size at the dissolution of potassium chloride.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042

Obviously, the ion size cannot become that small. Therefore, any decrease in ionic radii,

even in combination with re-arrangement of ions resulting in a more compact packing in

aqueous solution, is not sufficient to explain the volumetric behaviour of sodium chloride in

aqueous solutions.

Literature does not contain clear indications that ionic radii for the Na+, K+, and Cl- ions differ

between solid and in aqueous states, which is why it is quite safe to assume that decreases

in ionic radii do not contribute to volume shrinkage.

5.3 Distraction of Liquid Water Structure Due to Solvation

The third process that can contribute to volume shrinkage is partial distraction of liquid

water structure due to solvation (clustering of water molecules around ions).

Literature sources contain conflicting information regarding the size of hydrated ions. Earlier

sources indicate larger size of multilayer ion-water clusters (or hydrated ions) resulting from

the long range electrostatic ion-dipole forces, while more recent experimental results

suggest a different mechanism of ion-water interactions, as well as smaller amount of water

molecules bounded to ions [2]. In particular, for Group I cations and Group VII anions, only

the first layer of water around the ions is affected. Surprisingly enough, the amount of

bounded water molecules does not exceed 4-6 molecules even for ions with high surface

charge density. The new understanding of ion-water interactions definitely changes the

picture of hydrated ions.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042

In the following exercise, based on the acquired experimental data, I will try to estimate how

water structure modification (distraction) around ions can contribute to the observed

volume shrinkage. This mathematical exercise is not as straightforward as the previous two

and thus requires additional discussion regarding the structure of liquid water.

Literature sources [8, 12] indicate that the structure of liquid water is determined by

hydrogen bonding between the molecules. Various sources mention water clusters with a

number of empty cavities formed between the linked water molecules [12], although the

size of such clusters differs from source to source and does not seem to be well defined

experimentally. In any case, such partially empty structure of liquid water makes it less

dense than it would be in case of more efficient packing of molecules.

The diameter of a water molecule, represented as a sphere, is approximately 2.8 Å [8, 12].

Assuming the most efficient packing of such spherical molecules with 74% occupancy, one

can consider the most dense water structure and estimate the theoretical minimum of its

molar volume. The calculation in Appendix 7 shows that the molar volume of such “dense”

water is 9,35 cm3/mol. Published data [2] confirms that water molecules in first or maximum

second nearest layers surrounding the ions in aqueous solution are taken out from the usual

hydrogen bond controlled structure of the bulk water, and orientated towards the ions,

resulting in local water compaction around the ions.

In the following calculation (Appendix 7), I will try to estimate the amount of water

molecules orientated and bound to the sodium ion in order to simulate the observed

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
difference in partial molar volumes of sodium and potassium ions of approximately 8

cm3/mol in aqueous solution. It is assumed that more efficient packing of ions with 74%

occupancy occurs when water dissolves these solid salts.

Table 14: Number of H2O Molecules that Need to Be Orientated


Volume Number of
Theoretical
Volume of one water
Diameter water
Molar Volume of one mole molecules
of water Radius Packing shrinkage
volume of of one mole of when that need
molecule (literature) efficiency at 74%
liquid H20 sphere spherical packing to be
(literature) (m) of H 2O packing
(cm3/mol) (m3) particles efficiency orientated
(m) 3 efficiency
(cm /mol) is 74% around
3 (cm3/mol)
(cm /mol) Na+ ion
H2O 18,05 2,80E-10 1,40E-10 1,15E-29 6,92 9,35 38 % -8,71 -
+
Na - - 1,02E-10 4,44E-30 2,67 3,61 - 0,13 0,4

The calculation suggests that there should be only 0,4 molecules of water bound to sodium

ions to explain the difference in apparent molar volumes. This surprisingly low number is not

exactly the same (0,25 water molecules) as the one mentioned in [2], but at least it has the

same order of magnitude, which is a good result, taking into account a limited accuracy of

the simplified model and the experimental data.

Originally, in the above-mentioned calculation, for simplicity, I assumed that potassium ions

do not modify water structure. However, later, the validity of this assumption was confirmed

by experimental data [2]. The publication indicates that ions with smaller radii and greater

charge density can be classified as kosmotropes (e.g. sodium ion), while ions with greater

ionic radii and lesser charge density can be classified as chaotropes (e.g. potassium and

chloride ions).

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
According to [2], the strength of sodium ion-water interaction exceeds the strength of

hydrogen bonding, which is why sodium ion can modify water structure around itself. On the

contrary, the strength of potassium ion-water interaction does not exceed the strength of

hydrogen bonding, which is why potassium and chloride ions are not able to modify water

structure.

This essential difference explains why sodium chloride is able to modify water structure and

demonstrate a more pronounced tendency of volume shrinkage at dissolution than

potassium chloride does.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
6. Analysis of Volumetric Behaviour of Saccharides in Aqueous Solution

As shown previously, the apparent molar volumes of saccharides in aqueous solutions do not

differ significantly from their molar volumes in the crystalline state. The volumes of these

saccharides remain almost unchanged after they have been dissolved, which means that

volumes of water and saccharides are almost additive.

Such behaviour is different from the volumetric behaviour of salts. The root cause why salts

exhibited such behaviour was that there are contrasting forces of interaction between the

neighbouring particles in crystals lattice and in aqueous solution.

Literature sources suggest that the intermolecular interactions for saccharides are quite

different from salts. Both, structure of water in liquid phase, and structure of saccharides in

solid phase are governed by hydrogen bonding [8]. Therefore, hydrogen bonding remains

the main type of intermolecular interactions between sugar and water molecules in aqueous

saccharide solutions.

As long as all binary sugar-sugar, water-water, and sugar-water interactions are

predominantly controlled by hydrogen bonding, they are not expected to be significantly

different in strength. With relatively similar and homogenous intermolecular interactions,

there is no reason to believe that the volumetric behaviour of saccharides in aqueous

solutions should be abnormal. That is because the packing density of saccharides does not

change after dissolution, the molecular sizes of saccharides do not change, and they do not

modify the structure of water. Of these processes, changing of molecular sizes of saccharides

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
seems to be the least realistic, since molecular sizes are controlled by the covalent bonds,

which are significantly stronger than any of the intermolecular hydrogen bonds.

Therefore, it does not seem surprising that the volumes of crystalline glucose and sucrose

remain almost unchanged when they are dissolved in water, and that the apparent molar

volumes of saccharides in aqueous solutions do not differ significantly from their molar

volumes in a crystalline state.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
7. Conclusion

The first thing this investigation showed was that when salts were dissolved in water, their

molar volumes decreased. According to my laboratory experiments and calculations, the

volume of sodium chloride shrank by 31%, from 27,0 cm3/mol to 18,6 cm3/mol, and the

volume of potassium chloride volume shrank by 29%, from 37,6 cm3/mol to 26,7 cm3/mol.

These volume shrinkages were explained by increase in packing density of ions after

dissolution in water and distraction of liquid water structure due to solvation. The

calculations showed that the volume shrinkage of potassium chloride could be solely

explained by rearrangement of ions to maximise the efficiency of packing, while it was not

sufficient to explain the volume shrinkage of sodium chloride. Decrease of ionic radii of

sodium ions (if any) was not enough to explain the shrinkage either. In addition to the

rearrangement into a more efficient packing of ions, orientation of some water molecules,

nearest to sodium ions, resulted in local water compactions due to distraction of local water

structure. My calculations suggested that only 0,4 water molecules have to be orientated

around a single sodium ion, which is close to published experimental data [2].

The second thing that was found during the investigation was that volumes of saccharides

did not shrink as much as those of salts. In my laboratory experiments, the volume of

glucose shrank by 2%, from 116,7 cm3/mol to 114,8 cm3/mol, and the volume of sucrose

shrank by 6%, from 215,7 cm3/mol to 203,0 cm3/mol.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Since the main type of bonding present in both sugars and water is hydrogen bonding, there

is no reason why any major volume shrinkage should occur. There were, however, some

minor volume shrinkages. Overall, the two sugars did not exhibit great deviation from

volume additivity as the two salts did.

7.1 Further Questions

During the investigation, it became evident from published data, that the solubilities of

glucose and sucrose at room temperature are 91 g/100ml and 200 g/100ml respectively. The

maximum mass of any sugar dissolved in this experiment was only 30 grams per 100 ml of

water. Therefore, the conclusion with regard to the volumetric behaviours of sugars cannot

be applied to the whole range of concentrations of aqueous sugar solutions. Similar

experiments could be conducted at greater concentrations as a follow-up study.

In addition to that, it would be interesting to observe and analyse the behaviour of other

chemical compounds in aqueous solutions. It makes sense to study other soluble organic and

inorganic compounds in order to find out whether the volumes are additive or not and

further explore the reasons for the volumetric behaviours.

Finally, by increasing the accuracy of experimental data collection, it would be possible to

come up with an independent calculation of ionic radii.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
8. Bibliography (MLA)
1. Lide, David R.. CRC Handbook of Chemistry and Physics, 90th Edition. 90 ed. Boca
Raton: CRC, 2009.

2. Collins, Kim, George Neilson, and John Enderby. "Ions in water: Characterizing the
forces that control chemical processes and biological structure." Biophysical
Chemistry128 (2007): 95-104. Elsevier. Web. 17 Aug. 2010.

http://hwiki.fzk.de/wiki/images/2/2e/Collins_et_al.(2007)BC.pdf

3. Wikipedia contributors. "Ideal solution." Wikipedia, The Free Encyclopedia.


Wikipedia, The Free Encyclopedia, 23 Mar. 2010. Web. 17 Aug. 2010.

http://en.wikipedia.org/wiki/Ideal_solution

4. Стась, Н.Ф., and Л.Д. Свинцова. Химия растворов. Томск: Издательство ТПУ, 2006
(Russian)

5. Ergican, Erdogan. "Water Quality." Natura. Natura® Water, LLC, n.d. Web. 17 Aug.
2010. <naturawater.com/pdf/water-quality.pdf>

6. The World Factbook 2009. Washington, DC: Central Intelligence Agency,


2009.

https://www.cia.gov/library/publications/the-world-factbook/geos/xx.html#Geo

7. Graham, Ian, Barbara Taylor, John Farndon, and Chris Oxlade. "Jorden og livet."
Vitenskapens verden. Bath: Spektrum, 2006. 168. (Norwegian)

8. Mathlouthi, M, and J Genotelle. "Role of water in sucrose


crystallization." ElsevierCarbohydrate Polymers (1998): 335-342. AVH. Web. 29 Aug.
2010

9. R.D. Shannon, "Revised Effective Ionic Radii and Systematic Studies of Interatomic
Distances in Halides and Chalcogenides", Acta Cryst. A32 751-767 (1976)

http://abulafia.mt.ic.ac.uk/shannon/

10. Clugston, Mike. "Solids."Advanced Chemistry. New York: Oxford University Pr, 2000.
92-93.

11. Chaplin, Martin. "Water molecule structure." London South Bank University. N.p., n.d.
Web. 4 Aug. 2010. http://www.lsbu.ac.uk/water/molecule.html

12. Chaplin, Martin. "Water clusters (Overview)." London South Bank University. N.p.,
n.d. Web. 4 Aug. 2010. <http://www.lsbu.ac.uk/water/abstrct.html>

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
9. Appendices
Appendix 1

Preliminary Experiment
Research question:

How and why does the volume additivity of organic and non-organic compounds in an aqueous
solution differ from that of an ideal solution?

Variables:

Controlled Independent Dependent


Temperature Mass of a solute Mass of a 10 cm3 sample
Pressure
Amount of water
Purity of water
Purity of chemicals

Apparatus:
Note:
 Accurate scales
 Glass pipette Water temperature should
 Solute (NaCl for this experiment) be around 20-25 C.
 Distilled water
 Beakers Note:

Method: Maximum solubility of NaCl


in water is 357 g/L.
1. Fill four beakers with 100 cm3 of distilled water.
2. Add 10g of NaCl to the first one, 20g to the second one and 30g to the third one.
3. Leave fourth beaker as a control.
4. Carefully pipette 10 cm3 from each beaker and record the mass of a solution.
5. Repeat the steps two more times to acquire three readings.
6. Calculate densities

Data:

Mass of NaCl (g) Mass 1 (g) Mass 2 (g) Mass 3 (g) Average mass (g) Density (g/cm3)
0 9,970 9,980 9,990 9,980 0,998
10 10,69 10,72 10,71 10,71 1,071
20 11,25 11,18 11,25 11,23 1,123
30 11,77 11,77 11,82 11,79 1,179

Conclusion: The data shows that this experiment is likely to work.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Appendix 2

Calculating the Apparent Molar Volume of a Solute in


an Aqueous Solution at Infinite Dilution
Calculation of the apparent molar volume of a compound dissolved in water at infinite
dilution involves several graphical and analytical steps.

Derivation:

1. Find the percentage of mass of solute out from the total mass of a solution.
a.
2. Since the density for a particular is known, plot a graph which shows how
density changes with relationship to .
a. Plot on the x-axis and the density of a solution on the y-axis.
b. Plot a curve of best fit and note its function. Call it .
c. This curve will give the density of a solution at any concentration. However,
there is a limit to it, because the concentration cannot be negative and it
cannot be greater than the saturation point.
i. E.g. for NaCl,
3. Generate the values for and calculate the values for density for each
concentration using .
4. Calculate the values for apparent molar volumes at given concentrations that were
generated in the previous step using the following formula:

Note: – Volume, – percent mass, – Molar mass, – density.

5. Plot a graph which shows the relationship between the and the apparent
molar volume of a solute.
a. Plot on the x-axis and the apparent molar volume of solution on the
y-axis.
b. Plot a curve of best fit and note its function. Call it .
c. This curve will give the apparent molar volume of a solute at any
concentration, as long as the saturation point of a solute is not exceeded.
6. Calculate . This will give the apparent molar volume of a
solute at infinite dilution.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Appendix 3

Calculating the Apparent Molar Volume of NaCl


(Example, which shows how to use Appendix 2)
In order to calculate the apparent molar volume of sodium chloride at infinite dilution, it is necessary
to find a function, which describes the relationship between the mass percentage of sodium chloride
in solution and the density of a solution.

Density of an Aqueous Solution at Certain Concentration of Solute


%W(NaCl) (%) Average Density (g/cm3)
0,0000 0,998
4,791 1,028
9,121 1,062
13,069 1,092
16,696 1,121
20,034 1,148
23,114 1,174

Relationship between the Mass Percentage of NaCl in Solution and the


Density of a Solution

When such curve was obtained, it is possible to use the equation of a function to figure out the
density of an aqueous sodium chloride solution at desired concentrations, by plugging values of
concentration into the equation.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
In the table below, it is evident how the values for %W(NaCl) were generated, and the corresponding
densities calculated using the equation of a function acquired from the graph above. After that, a
series of calculations is performed to calculate the apparent molar volume of sodium chloride in
aqueous solution. The assumption is that the density of water stays constant, because the density of
water will not be affected at infinite dilution.

Generating Values for Density of a Solution and Calculating Apparent Molar Volume
%W(NaCl) NaCl Density Volume of 100g Volume of Water Apparent Molar Volume
(%) (g/cm3) Solution (cm3) (cm3) (cm3/mol)
0,000 0,998 100,210 100,210 #DIV/0!
1,000 1,005 99,545 99,208 19,657
2,000 1,011 98,879 98,206 19,663
3,000 1,018 98,214 97,204 19,671
4,000 1,025 97,549 96,202 19,683
5,000 1,032 96,885 95,200 19,698
6,000 1,039 96,222 94,198 19,717

Now that the values for mass concentration of NaCl and the apparent molar volume of NaCl in
solution are known, it is possible to make a curve fit and calculate the approaching value of apparent
molar volume of NaCl.

Finding the Apparent Molar Volume of NaCl at Infinite Dilution

In order to obtain an accurate value for the apparent molar volume of NaCl at infinite dilution, it is
necessary to manipulate the data slightly and filter out the points, which might seem anomalous.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Appendix 4

Calculating the Percent of the Volume in a Unit Cell


of Sodium or Potassium Chloride Occupied by
Spherical Ions
In order to calculate the percent of the volume in a unit cell of sodium or potassium chloride
occupied by spherical ions, it is necessary to use the formula below.

Derivation:

1. NaCl and KCl structures consist of two interpenetrating face-centred cubic arrays.
2. There are 4 ions in one face-centred cubic array.
a.
3. There are 2 such interpenetrating arrays in one unit cell of NaCl or KCl.
a.
4. It can be assumed that the ions are spherical. Their volume is the same as the volume
of a sphere.
a.
5. Therefore, the volume of 8 spherical ions is .
6. It is now necessary to find the volume of a unit cell of NaCl and KCl. This can be done
by taking a cube of a length of a unit cell length.
a. , where is the length of a unit cell.
7. The length of a unit cell is the sum of diameters of two ions in a unit cell, which is also
known as lattice constant.
a. Therefore, .
8. To find the percent of the volume in a unit cell of sodium or potassium chloride
occupied by spherical ions, it is necessary to find the ratio between the volume of
ions and the volume of a unit cell.
a.

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Appendix 5

Calculating the Molar Volume of a Solute in Crystalline


State and the Percent Shrinkage of Volume of a Solute
To calculate the molar volume of a solute in crystalline state, the two things that are
necessary are the molar mass of a solute and the density of a solute in crystalline state.

Derivation:

1. It is possible to calculate the molar volume of a solute in a crystalline state using only
two values, molar mass of a solute and the density of a solute in crystalline state.
2. The formula is therefore: .

To calculate the percent shrinkage of the volume of a solute, the two values which are
needed are the molar volume of a solute in crystalline state and the apparent molar volume
of a solute dissolved in water at infinite dilution.

Derivation:

1. Calculate the molar volume of a solute in crystalline state using the formula above.
a.
2. Calculate the apparent molar volume of a solute dissolved in water at infinite dilution
using a method in Appendix 2.
a.
3. Calculate the percent shrinkage of the volume of a solute using a formula below:

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Appendix 6

Calculating the Apparent Molar Volumes of Anions and


Cations in Solution
This assumption is that the difference in apparent molar volumes of the two salts is caused
by the presence of different cations. If the potassium ion is substituted with a sodium ion,
the volume of a solution should shrink by 8 cm3. Since the anions are the same, they are the
starting point of this calculation.

Derivation:

1. The initial compound that is dissolved in water is potassium chloride. It’s apparent
molar volume at infinite dilution is 26,66 cm3/mol.
2. It is now necessary to calculate the percentage of volume 4 anions occupy out of the
whole volume of 8 ions (cations and anions).

Note: – total volume of 8 ions (see Appendix 4), - percentage of


volume occupied by spherical anions.

3. Find the volume of anions in one mole of aqueous ionic compound.

Note: – Apparent molar volume of an ionic compound at infinite


dilution, - percentage of volume occupied by spherical anion.

4. Find the volume of cations by subtracting the volume of anions from the apparent
molar volume of a compound at infinite dilution.
a.
5. By plugging in the numbers, it becomes evident that the value for the volume of one
of the cations is absolutely wrong (Na cation in this case – 0,17 cm3/mol).

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Chemistry Extended Essay
Candidate Name: Alexander Zakharov
Candidate Number: 000862-042
Appendix 7

Calculating the Number of H2O Molecules that Need to


Be Orientated towards Sodium Ion
Since more efficient packing of ions and a decrease in ionic radius of a cation is not sufficient
to explain the volume shrinkage of sodium chloride, there has to be something else
happening. This process is orientation of water molecules toward the sodium ion, because it
is a kosmotrope.

The process involves a comparison of volume shrinkages of water and sodium ions.

Derivation:

1. Calculate the molar volume of water using its molar mass and density.
a.
2. Calculate the volumes of one molecule of water (assuming it is a sphere) and one ion
of sodium using a formula below.
a.
3. Calculate the volume of one mole of molecules of water and sodium ions.
a.
4. Calculate the volume of one mole of molecules of water and sodium ions if their
packing efficiency was 74%.
a.
5. Calculate by how much the volume of water would shrink if its packing efficiency
changed from 38% to 74%.
a.
6. Calculate the number of water molecules that need to be orientated towards a
sodium ion, so that its volume shrinkage is zero.
a.
b.
c.
i. Note: – number of water molecules.

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