Best IB Resources Website
Sell your IB Docs (IA, EE, TOK, etc.) for $10 a pop!
Best IB Resources Website
Nail IB's App Icon
Chemistry SL
Chemistry SL
Sample Extended Essays
Sample Extended Essays

Skip to

Table of content
Research question
Rationale
Background information
Variables
Hypothesis
Materials required
Risk assessment
Procedure
Qualitative data
Quantitative data
Data processing
Choice of axes
Conclusion
Evaluation
References
Appendix-

Effect Of Composition Of A Mixture On It’s Freezing Point

Effect Of Composition Of A Mixture On It’s Freezing Point  Reading Time
21 mins Read
Effect Of Composition Of A Mixture On It’s Freezing Point  Word Count
4,082 Words
Candidate Name: N/A
Candidate Number: N/A
Session: N/A
Personal Code: N/A
Word count: 4,082

Table of content

Research question

Is there any correlation between the freezing point of a mixture of naphthalene and 4-nitrophenol and the composition of the mixture (in terms of mole-fraction), determined using temperature versus composition diagram?

Rationale

Inquirer and reflective are the two best profiles that describes me as a learner. I always believe that production or pursuit of knowledge begins from something we observe and want to explore more. This essay has also been a similar journey. I would like to begin with an anecdote; during my visit to Kashmir (the most popular hill station in India), I observed something really unusual. Local habitats were spreading common salt on the ice to melt it. The reason being unknown, I explored more and came to know that addition of salt can depress the freezing point of ice. Being an inquirer, I wanted to check it myself; I took two bottles –one with normal water and other with salt water; kept both of them in the refrigerator. As expected, after a while, I found that the pure water was converted to ice while the salt water not. This evoked me to search more. I made an effective search from reliable and credible secondary sources and came to know about the addition of impurity to change the freezing point of mixtures. The immediate question I had – What is the application or use of this phenomenon? Further exploration on the application of this topic led me to know about the existence of eutectic mixture, which is mainly a mixture of two solids in such a ratio so that the freezing point of the mixture in that ratio is lower than the freezing point of the pure component in the mixture. Learning from a text book on Physical Chemistry by Engel and Red exposed me to the fact that the mixture of poly-nuclear aromatic hydrocarbon and phenolic compounds behave as eutectics. Immediately, a consultation with my laboratory technician, I got to know that we have naphthalene (binuclear aromatic hydrocarbon) and phenol in our school laboratory, which can be the perfect choice of two materials for making an eutectic mixture. Thus, I decided to conduct my Extended Essay in Chemistry to address the research question stated below:

 

Is there any correlation between the freezing point of a mixture of naphthalene and 4-nitrophenol and the composition of the mixture (in terms of mole-fraction), determined using temperature versus composition diagram?

Background information

Freezing

Freezing is the process of converting a substance from liquid state to solid state. Freezing of a substance in the liquid state will occur at a constant value of temperature and that is considered as the freezing point. During freezing there exists equilibrium between the solid and the liquid phase.

Principle of determination of freezing point

During any phase change like freezing, the temperature of the system remains unchanged until the phase change is completely over. The heat lost by the system is lost in the form of latent heat and does not decrease the temperature of the system. During freezing, the heat lost by the system is manifested in decreasing the disorderness or entropy of the system as it changes from a more disordered liquid state to a less disordered solid state.

Figuer 1 - Cooling Curve Diagram (The Figure Is Made By Me Using MS Paint)
Figuer 1 - Cooling Curve Diagram (The Figure Is Made By Me Using MS Paint)

To determine the freezing point, the component is taken in the liquid state and then allowed to cool. The temperature of the system (whether one single component or a homogenous mixture of two components) is recorded at regular intervals of time unless the entire system gets converted into solid. A graph is plotted with temperature along the y axes and time along th e x axes. In the graph, a straight line parallel to the x axis is obtained. This line is extrapolated to intersect the y axes and the temperature at the intersection point is taken as the freezing point of the system.

 

In the above figure (Figure - 1), the line XY represents the compound in liquid state while the line WZ represents the compound in solid state. The line YW represents the coexistence of both the solid and liquid phase in equilibrium and thus denotes the phenomenon of freezing.

Mole-fraction

For a mixture of two components A and B with number of moles nA and nb,

 

Mole-fraction of A (XA) = \(\frac{^nA}{^nA+^nB}\) ;  mole-fraction of B (XB) = \(\frac{^nB}{^nA+^nB}\)

 

Sum of mole-fraction = XA + XB = 1

Eutectic point

Figure 2 - Eutectic Temperature Phase Diagram
Figure 2 - Eutectic Temperature Phase Diagram

There are certain mixture of two solid components which exhibits a freezing point of a much lower value than the freezing point of the individual pure components. For example a mixture of Sn and Pb exhibits a freezing point of  183°C at a composition of 62% of Sn and 38% of Pb by mass and this freezing point is much lower than the freezing point of the pure components (Sn = 232°C and Pb = 327°C). Such points in the temperature versus composition graphs are known as eutectic points and the composition of the mixture at those points is known as the eutectic composition while the temperature is known as the eutectic temperature. Although, the scientific reason behind existence of such points is still not clear, yet some researches claim that it is due to the variation in the crystal structure of the compounds in the pure form and the solids formed by cooling of the molten mixture at the eutectic point.

Naphthalene

Refer to Appendix A-1

 

nitrophenol: Refer to Appendix A-1

Effect of foreign substance on freezing point on a pure compound

To analyse or understand the variation of freezing point of a mixture of two components, we need to first understand how the freezing point of a pure compound will change if a foreign substance is added to it. Addition of non-volatile solutes to a pure solvent decreases the freezing point which is very well defined in Raoult’s law of colligative properties. For example, the freezing point of an aqueous solution of NaCl would be lower than the freezing point of pure water.

 

Freezing is basically converting a substance from liquid state to solid state. In this process, the molecules in the liquid state are brought closer to each other to decrease the intermolecular distance between them. This is achieved by decreasing the temperature and thus reducing the average kinetic energy of the molecules which in turn slows down the motion of the molecules and brings them closer.

 

If we are cooling pure water, as we decrease the temperature, the water molecules will come closer and finally gets converted into solid state at it’s freezing point. But, if some other substance like NaCl is present along with water in the system, these particles will come in between the water molecules when they are trying to come closer and hence inhibit them from coming closer and go into the solid state. To counteract this interference of NaCl, we need to reduce the motion of all the particles in the system to a greater extent and thus decrease the temperature to a greater extent. Thus, the freezing point of the system decreases. Thus, in short as the amount of impurity added to a pure component increases, the freezing point decreases more.

Thermodynamics of freezing

Freezing is an exothermic process. Hence the value of enthalpy change (∆H) is negative. During freezing, liquids are converted to solid, disorderness of the system decreases; value of entropy change (∆S) is negative.

 

 ∆G = ∆H - T∆S

 

Since ∆S is negative, the term (-T∆S) becomes positive. So, the value of Gibb’s free energy change(∆G) would be negative only if the magnitude of ∆H exceeds the magnitude of T∆S. Thus, as the temperature decreases, the value of ∆G becomes less positive or more negative and the process becomes more spontaneous.

 

To simplify, we may say that as the freezing point decreases, the process of freezing becomes more thermodynamically favoured.

Gibb’s phase rule

Gibb’s phase rule states that:  F = C-P+1 (assuming pressure to be constant).

 

F = Degrees of freedom

 

C = number of components

 

P = number of phases (solids, liquids or gases).

 

The degrees of freedom of a particular point in a temperature versus composition graph represent the number of intensive (mass independent) variables which we can alter for that particular point. For example, if the degrees of freedom calculated for a particular point is 1; it means that even if we change a particular variable like temperature or mass, the system will still be in the same phase (solid/liquid/gas).

Alternative method

In order to study the variation of the freezing point of a mixture of two solids against the composition of the mixture, we may use the resistivity method. We have to take the mixture, allow it to cool and measure the resistance at regular intervals of time. At the freezing point, the mixture will get converted from the liquid to solid state, the ions in the system will stop moving and the value of resistance will increase sharply. Thus, if we plot the values of resistance of the system against temperature, a sharp jump will be observed in the graph indicating the freezing point of the liquid.

Figure 3 - Resistance Of The System Against Temperature (Made By Me Using MS Paint)
Figure 3 - Resistance Of The System Against Temperature (Made By Me Using MS Paint)

The method is appropriate if both the components in the mixture are ionic in nature. In the current investigation, naphthalene and 4-nitrophenol have been used and both of them are organic and covalent compounds. So, this method was not used.15

Variables

Independent Variable – Composition of the mixture

Different ratios of masses were taken for naphthalene and 4-nitrphenol measured using a mass balance and the moles were calculated. Then the formula for mole fraction was used to calculate the mole fraction of 4-nitrophenol. The mass ratio between naphthalene and 4-nitrphenol was varied. The substances were mixed in the following ratios-

Mass of Naphthalene in grams/ ±0.01
Mass of 4-nitrphenol grams/ ±0.01
Mass Ratio
5.00
0.00
5:0
4.00
1.00
4:1
3.00
2.00
3:2
2.00
3.00
2:3
1.00
4.00
1:4
0.00
5.00
0:5
Figure 4 - Table on Mass Of Naphthalene, 4-Nitrophenol And Their Ratios

Dependent – Freezing temperature of the mixture of naphthalene and 4-nitrophenol.

Stainless steel temperature probe and Lab Quest was used to measure the temperature of the mixture at intervals of 30 seconds. The temperature was recorded against time for 10 minutes and the graph was plotted, the plateau region or the region where the temperature did not change for a few minutes was considered as the freezing temperature.

 

List of controlled variables

  • Pressure, since freezing point depends on the pressure. All experiments done under atmospheric pressure.
  • Initial temperature of the substances was kept the same using a water bath, all experiments started from 1100C.
  • Total Mass of the mixture was kept the same in all experiments, using a mass balance (addition is always 5 grams).
  • Surface area, since heat loss depends on the surface area and can change the rate of heat loss. (Same test-tube used everywhere)
  • Cooling process, in all experiments the mixture was cooled using the same process.

Hypothesis

Null hypothesis

I hypothesize that there is no correlation between the independent variable- Composition of the mixture, and the dependent variable- freezing temperature of the mixture of naphthalene and 4-nitrophenol.

 

Alternative hypothesis

I hypothesize that there is a strong correlation between the independent variable-Composition of the mixture, and the dependent variable- freezing temperature of a solid solid binary mixture of naphthalene and 4-nitrophenol.

Materials required

(Refer to appendix A2 for material required)

Apparatus required

(Refer to appendix A3 for apparatus required)

Risk assessment

Substance
Hazard
Safety Precaution
Naphthalene
It is a heat sensitive substance and flammable. Exposure to naphthalene is associated with hemolyticanemia and damage to the liver.
Did not heat it directly during the experiment, a water bath was used to avoid it to catch fire, use of mask and gloves.
4-nitrophenol
Acute (short-term) inhalation of 4-nitrophenol in humans causes headaches, drowsiness, nausea corrosive in nature.
Ensure adequate ventilation. Use safety goggles and wear impervious protective clothing, including boots, gloves, lab coat.
Figure 5 - Table On Safety Precautions

(For further information refer to appendix A5)

Ethical considerations

  • Minimum amount of chemicals were used.

Environmental concerns

  • There were no toxic emissions to harm the environment during the investigation.
  • All the waste was safely disposed in the waste bin and diluted or added water to it before disposal so that the environment is not harmed.

Procedure

Calibration of temperature probe -Refer to appendix A5

 

Calibration of the mass balance -Refer to appendix A5

 

Primary procedure

  • 5 ± 0.01 grams of pure naphthalene was weighed on a watch glass using an electronic mass balance,
    put in a test tube fitted with cork, using a spatula and a temperature probe was inserted in the test-tube.
  • The test-tube was immersed in the water bath (as shown in Figure-4) and heated till the temperature on temperature probe was recorded to be 110 ± 0.010C and the entire pure naphthalene was in molten state.
  • The test tube was removed from the water bath immediately and kept in a test tube rack to cool down.
  • The temperature was measured at intervals of 30 ± 0.01 seconds for 10 minutes.
  • The same process was repeated for other mixtures – 4.00 ± 0.01 g of naphthalene and 1.00 ± 0.01 g of 4-nitrophenol, 3.00 ± 0.01 g of naphthalene and 2.00 ± 0.01 g of 4-nitrophenol, 2.00 ± 0.01 g of naphthalene and 3.00 ± 0.01 g of 4-nitrophenol, 1.00 ± 0.01 g of naphthalene and 4.00 ± 0.01 g of 4-nitrophenol and 5.00 ± 0.01 g of 4-nitrophenol.
Mass of Naphthalene in grams/ ±0.01
Mass of 4-nitrphenol grams/ ±0.01
Mass Ratio
5.00
0.00
5:0
4.00
1.00
4:1
3.00
2.00
3:2
2.00
3.00
2:3
1.00
4.00
1:4
0.00
5.00
0:5
Figure 6 - Table On Mass Of Naphthalene, 4-Nitrophenol And Their Ratios
Figure 7 - Image Of The Experimental Set Up Taken By Me Using I-Phone 7 Plus
Figure 7 - Image Of The Experimental Set Up Taken By Me Using I-Phone 7 Plus

Qualitative data

  • The appearance of the mixture of naphthalene and 4-nitrophenol was pale yellow when molten. As the mass percentage of 4-nitrophenol was increased, the colour became darker when molten.
  • While heating the mixture of the solid mixture, liquid droplets were formed at the upper part of the test tube, which solidified to shinning needle like crystalline structures while cooling as shown in the image below:
Figure 8 - Appearance Of Crystals At The Upper Part Of The Test Tube (Image Was Captured In My I-Phone 7 Plus While Doing The Experiment)
Figure 8 - Appearance Of Crystals At The Upper Part Of The Test Tube (Image Was Captured In My I-Phone 7 Plus While Doing The Experiment)
  • It was very difficult to remove the temperature probe from the test tube, once the mixture was solidified. The mixture was melted again to bring it out.
  • The appearance of the solid mixture before heating them to melt was crystalline and shinning. While on solidification during cooling, it appeared to be lumpy and much less shinny.

Quantitative data

Raw data

Figure 9 - Table On Temperature Change With Time For 5 Grams Of Naphthalene And 0 Grams Of 4-Nitrophenol
Figure 9 - Table On Temperature Change With Time For 5 Grams Of Naphthalene And 0 Grams Of 4-Nitrophenol
Figure 10 - Variation Of Time (Seconds) Against Temperature Of Mixture Of 5 Grams Of Naphthalene And 0 Grams Of 4-Nitrophenol.
Figure 10 - Variation Of Time (Seconds) Against Temperature Of Mixture Of 5 Grams Of Naphthalene And 0 Grams Of 4-Nitrophenol.

In the graph above, line AB the represents pure naphthalene in the liquid state, CD represents naphthalene in the solid state and line BC represents equilibrium between naphthalene in solid state and naphthalene in liquid state. Hence, the temperature corresponding to the line BC (80C) is considered as the freezing point because during freezing the temperature of the mixture is supposed to remain constant over a period of time until the entire liquid has not been converted completely into solid state.

 

Refer to Appendix A-6  for other raw data tables and Appendix A-7 for other graphs.

Data processing

Mass of 4-nitrophenol/ ±0.01 grams
Mass of Naphthalene/ ±0.01 grams

Mole fraction of 4-nitrophenol (XA)

Mole fraction of naphthalene (XB

Freezing point/ ±0.1°C

Percentage Error (%)/ ± 10-2

0.00
5.00
0.00
1.00
80.0
0.12
1.00
4.00
0.19
0.81
58.0
0.17
2.00
3.00
0.37
0.63
35.0
0.28
3.00
2.00
0.58
0.42
55.0
0.18
4.00
1.00
0.79
0.21
68.0
0.14
5.00
0.00
1.00
0.00
105.0
0.95
Figure 11 - Table On Mole Fraction With Freezing Point And Errors

Mole fraction calculation for 1 gram of 4-nitrophnol and 4 grams of naphthalene

 

Moles of 4-nitrophenol(nA)

 

\(=\frac{mass}{molar \ mass}=\frac{1.00}{139.11}\) = 0.0072

 

Moles of 4-nitrophenol (nB)

 

\(=\frac{mass}{molar \ mass}=\frac{4.00}{128.17}\)= 0.031

 

Mole-fraction of 4-nitrophenol (XA)\(=\frac{^nA}{^nA+^nB}=\frac{0.0072}{0.0072+0.031}\) = 0.19

 

Mole-fraction of naphthalene (XB) =1- XA=1 - 0.19 = 0.81[since,XA+X= 1]     

                            

Sample Calculation for determination of random error and percentage error in freezing point

 

Freezing point (x) = 58.00 °C;  average uncertainty in temperature(∆x) = ± 0.1

 

Random error \(\frac{Δx}{x}=\frac{0.1}{58.00}\)= 0.001724

 

Percentage error = Random error × 100 = 0.001724 X 100 = 0.17 (approx.)

 

Sample calculation of uncertainty in mole-fraction of 4-nitrophenol

 

For 1.00 g of 4-nitrophenol and 4.00 g of naphthalene,

 

nA =0.0072 ± 0.01 ; nB =  0.031 ± 0.01 [uncertainties in mass and moles are considered to be identical]

 

n = total number of moles = nA + nB = 0.0072 + 0.031 = 0.0382 ± (0.01 + 0.01) = 0.0382 ± 0.02

 

\(\)XA=\(\frac{^nA}{^nA+^nB};\)

 

\(\frac{ΔX_A}{X_A}=\frac{Δn_A}{n_A}+\frac{Δn}{n}=\frac{0.01}{0.0072}+\frac{0.02}{0.0382}\) = 0.19

 

ΔXA = 0.19 X XA= 0.19 X 0.81 = ±0.35

Data analysis

Figure 12 - Variation of Mole Fraction Of 4-Nitrphenol Against Freezing Temperature Of Mixture Of Naphthalene And 4-Nitrophenol.
Figure 12 - Variation of Mole Fraction Of 4-Nitrphenol Against Freezing Temperature Of Mixture Of Naphthalene And 4-Nitrophenol.

XA = mole-fraction of 4-nitrophenol

 

XB = mole-fraction of naphthalene

 

A= point indicating freezing temperature of pure naphthalene

 

E =eutectic point

 

C = point indicating freezing temperature of pure 4-nitrophenol

 

AEB = Liquidus  and HEI = solidus

Choice of axes

The mole fraction of 4-nitrophenol is plotted along the x axes; as we move from left to right along x axes, mole fraction of 4-nitrophenol increases (XA=0 at point D to XA=1 at point E) and mole-fraction of naphthalene decreases (XB = 1 at point D and XB =0 at point E).  The uncertainty in x axes are not considered as it differs for each data points.

 

The freezing temperature (± 0.1 C) is plotted along the y axes as it is the dependent variable.

Best fit lines and the intersection point E

The two straight lines intersect each other at the point E. This point E is thus considered as the eutectic point of the mixture. A perpendicular is drawn from the point E which meets x axes at 26.0  and a perpendicular drawn from the point E meets y axes at 0.45.

 

At eutectic point(E),

 

Freezing temperature (Te) = 26.0°C

 

Mole-fraction of 4-nitrophenol (XA) = 0.45

 

Mole-fraction of naphthalene (XB) = 1-0.45 = 0.55

 

It clearly means that the mixture of naphthalene and 4-nitrophenol will exhibit the lowest possible freezing point if they are mixed in the ratio 0.55:0.45 (naphthalene:4-nitrophenol)  in terms of moles and the value of the lowest possible freezing point is 26.0C

Application of phase rule at the eutectic point and its interpretation

Applying Gibb’s phase rule to the eutectic point:

 

F= C-P+1

 

At the eutectic point, there is a equilibrium as shown below:

 

Mixture of naphthalene and 4-nitrophenol (liquid)  Napthalene(s) + 4-nitrophenol(s)

 

It means that at the eutectic point, the three phases- mixture of naphthalene and 4-nitrophenol in the liquid state, solid naphthalene and solid 4-nitrophenol co-exists.

 

So, number of phases (P) = 3

 

Number of components = 2; naphthalene and 4-nitrophenol

 

Hence, F = 2-3 + 1 =0

 

It means that at the eutectic point, there is no degree of freedom. It cannot be shifted either along the x axes or along the y axes; there is only one single and fixed composition of the mixture at which the freezing point will attain the lowest value; in case we change the composition or mole fraction of 4-nitrophenol the point will shift either to the left or right of the x axes and the equilibrium between the three phases – mixture of napthalene  and 4-nitrophenol in the molten state, solid naphthalene and solid 4-nitrophenol will be lost.

Description of the lines AEB(liquidus) and HEI(solidus)

The region above the line AEB represents the mixture of naphthalene and 4-nitrophenol in the molten state; it means that for each and every values of mole fraction in the x axes if the temperature is above the value on the line AEB, the mixture will be in the molten state. Similarly, the region below the line HEI  represents the mixture of solid naphthalene and solid 4-nitrophenol. It means that for all values of mole fractions of 4-nitrophenol along the x axes, the mixture will contain both the components in solid state, if the temperature of the mixture is below the eutectic point (26.0C). The line AEB represents the liquidus as it represents the mixture in molten state above it while the line CD is known as solidus as it represents the mixture in solid state below it.

Significance of the points D and E

Point D

Mole fraction of 4-nitrophenol (XA) = 0

 

Mole –fraction of naphthalene (XB)

 

= 1 – XA = 1-0 =1

 

It means that at point X, the compound is pure naphthalene.

 

Thus, point A on the y axes will represent the freezing point of pure naphthalene.

 

According to the graph,

 

Freezing point of pure naphthalene

 

( T0Bobserved) = value of y axes at point A = 80.0°C

 

Literature value of freezing point of pure naphthalene

 

( T0Bcaculated) = 80.2°C

 

Percentage error


\(=\frac{mod(observedvalue -calulatedvalue)}{calculatedvalue}\) X 100

 

\(=\frac{mod(80.2-80.0)}{80.2}\)X100 = 0.25

 

 

Point E

Mole fraction of 4-nitrophenol (XA) = 1

 

Mole –fraction of naphthalene (XB)

 

= 1 – XA = 1-0 = 1

 

It means that at point X, the compound is pure 4-nitrophenol.

 

Thus, point C on the y axes will represent the freezing point of pure 4-nitrophenol.

 

According to the graph,

 

Freezing point of pure 4-nitrophenol

 

( T0Aobserved)= value of y axes at point C = 105.0°C

 

Literature valueof freezing point of

 

pure 4 –nitrophenol ( T0Bcaculated) = 113.0°C

 

Percentage error

 

\(=\frac{mod(observedvalue-calculatedvalue)}{calculatedvalue}\)X100

 

\(=\frac{mod(105.0-113.0)}{113}\)X 100  = 7.7

 

Thus, the values of freezing point  of pure naphthalene and 4- nitrophenol as calculated from the graph are 80.0°C ± 0.25% and 105.0°C ± 7.07% respectively

Scientific justification

Explanation behind the line AG

At point A, the system is pure naphthalene and thus it shows the freezing point of the pure component naphthalene. As we are adding more 4-nitrophenol into it, the process of freezing becomes difficult and thermodynamically unfavourable. The presence of molecules of 4-nitrophenol in between two molecules of naphthalene inhibits them from coming closer and go into the solid state.  Since, for freezing both ∆H and ∆S are negative, the process becomes more spontaneous with decrease of temperature. (Refer to Page- 9, 2.7). Thus, as the mass of 4-nitrophenol added increases from 0.00 g to 2.00g, freezing point decreases from 80.00C to 35.0°C to make the values of ∆G more negative and hence the process more thermodynamically favourable.

 

Explanation behind the line BF

Similarly, at point B (mole fraction of 4-nitrophenol=1), the system is pure 4-nitrophenol and thus the value in y axes represents the freezing temperature of pure 4-nitrophenol. As we are decreasing the mole fraction of 4-nitrophenol, we are basically increasing the mole fraction (or amount) of naphthalene. Here, since the amount of 4-nitrophenol is more and that of naphthalene is less, we may consider the former to be a pure component and the latter to be an impurity. Thus we may explain in the same way(as we did for AG), that amount of impurity (naphthalene ) increases, freezing point decreases to make the value of ∆G more negative and the process more feasible.

 

Reference to a secondary source

Pure Ibuprofen has a freezing temperature of 76.0°C and pure Thymol has a freezing temperature of 52.00C, whereas together the composition in the ratio of 2:3 has a freezing temperature of 32°C which is the eutectic point.

Conclusion

The basic aim of the investigation was to address the research question-

 

Is there any correlation between the freezing point of a mixture of naphthalene and 4-nitrophenol and the composition of the mixture (in terms of mole-fraction), determined using temperature versus composition diagram.

  • The freezing point of the mixture decreases from 80.0 ± 0.1 °C (freezing point of pure naphthalene) to 35.0 ±0.1°C as the mole fraction of 4-nitrophenol increases from 0.00 to 0.37, and the mole fraction of naphthalene decreases from 1.00 to 0.63.
  • Then the freezing point increases from 55.0 ±0.1°C to 105.0 ± 0.1°C (freezing point of pure 4-nitrophenol) as the mole fraction of 4-nitrophenol increases from 0.58 to 1.00  and the mole fraction of naphthalene decreases from 0.42 to 0.00.
  • The mixture exhibits the existence of a eutectic point at a temperature of 26.0°C and the eutectic composition of the mixture being 45% of 4-nitrophenol and 55% of naphthalene in terms of number of moles. The existence of this point indicates that the lowest possible freezing point of the mixture is 26.0°C, which is much lower than the freezing point of the pure components.
  • A solidus (HEI) has been obtained in the graph which indicates that the mixture will be always in the solid phase if the temperature is below 26.0C (eutectic temperature).
  • Similarly, a liquidus exists in the graph (AEB) which indicates the values of temperature for each and every composition of the mixture above which the mixture would be in the molten state.
  • As confirmed from the qualitative observation, the appearance of the mixture in solid state when pure components are mixed and that obtained after cooling of the molten mixture were significantly different; it confirms that the crystalline property of the components changes when they are mixed together.
  • The eutectic point is invariant in nature and has zero degrees of freedom. It indicates that there is only one such point in the entire graph and it represents an equilibrium between the molten mixture and the individual component in solid state.
  • The variation in the freezing point is mainly described or justified by the scientific fact that as we add impurity to a pure component, freezing becomes thermodynamically unfavourable. So, temperature is decreased to make the values of ∆G more negative and the process more feasible.
  • As per the above discussion suggests, I would accept my alternate hypotheses confirming a significant correlation between the freezing point of the mixture and the mole fraction of 4-nitrophenol in it.

Evaluation

Sources of error and improvements

Random error

  • The major source of random error in the investigation may be uncertainty in recording the temperature at an interval of 30 seconds. To avoid this, a temperature probe and a Lab Quest was used and the time interval was set at 30s.
  • Random errors are also associated with the uncertainty of the apparatus used like electronic mass balance, temperature probe. To avoid this, repeated readings have been taken and average values are considered.

 

Systematic error

  • 4-nitrophenol may undergo aerial oxidation to form quinones.Thus, it is important to ensure that 4-nitrophenol is not exposed to air for longer time period. In order to do this, the test tube containing the mixture was fitted with a cork having a hole to insert the temperature probe.
  • Naphthalene is a sublimable solid. If kept open, it can get converted directly into vapour. To ensure this, the naphthalene was not kept open in the air for a longer time period.
  • Although, both the solids –naphthalene and 4-nitrophenol were taken in the test tube and mixed with a glass rod before the test tube was transferred into the water bath for heating, it cannot be claimed without doubt that the solid mixture taken was homogenous.

Limitations

  • Although, naphthalene and 4-nitrophenol have been assumed to not react with each other chemically, certain findings question the validity of this assumption. The freezing point of the mixture containinggrams of naphthalene and 1g of 4-nitrophenol is calculated as 67.9C (refer to Appendix-A.8) while the observed value is 58.0°C. It clearly indicates that, naphthalene has reacted with 4-nitrophenol to form an addition compound. Thus, we cannot consider the mixture to be ideal in nature.
  • The co-efficient of eutectic mixture (keutectic) was calculated according to the following formula.

 

keutectic = \(\frac{^Te}{T^0_{napthalene}+T^o_{4-nitrophenol}}=\frac{26.6}{(80.0+105.0)}\) = 0.14

 

The accepted value of co-efficient of eutectic temperature is 0.25 to 0.49. Hence, the experimentally calculated value of coefficient of eutectic temperature is much lower than the lowest acceptable value and does not fall within the accepted range. This finding invariably questions our claim to consider the mixture of naphthalene and 4-nitrophenol as a eutectic system.

Strengths

  • The magnitude of standard deviation is quite low and thus indicates a high value of precision of the experiment.
  • The magnitude of percentage error is also not significantly high and hence indicates an appreciable accuracy of the investigation.
  • The entire research methodology has considered multiple sources of error and enough modifications in the procedure have been done to minimise them.
  • Appropriate apparatus have been used and in an effective manner.
  • Despite being a stating a correlation between the variables in the investigation, an attempt to explain them using scientific facts has been done.
  • Citation has been done to acknowledge the sources, the information or ideas are borrowed from.

Further scope of investigation

While doing the research, I came to know that the type of crystalline structure the components show in the pure form and in the solids formed at the eutectic point are different; it means at eutectic point the crystalline structure of the components differ from the original ones. I would like to conduct an investigation to study how the crystal structure of the solids changes when they form an eutectic mixture. It can be done if we study the crystal parameters (shape of crystals, distance between atoms) of the pure components and the solids obtained at the eutectic point using X ray diffraction study.

References

  • Boundless.“Boundless Chemistry.” Lumen Learning, Lumen, courses.lumenlearning.com/boundless-chemistry/chapter/phase-changes/. Accessed on February 13th 2018
  • “Changes of Phase (or State).” Changes of Phase, Heat, Temperature | Zona Land Education, zonalandeducation.com/mstm/physics/mechanics/energy/heatAndTemperature/changesOfPhase/changeOfState.html. Accessed on 29th june 2018.
  • “Freezing Point of Naphthalene Lab Answers.” SchoolWorkHelper, SchoolWorkHelper, schoolworkhelper.net/freezing-point-of-naphthalene-lab-answers/. Accessed on November 12th 2018
  • “Gibbs' Phase Rule.” Gibbs' Phase Rule, kj-gibbs.uio.no/phase_rule.html. Accessed on January 5th 2019.
  • “Heat, Temperature, and Conduction.” What Is Density? | Chapter 3: Density | Middle School Chemistry, http://www.middleschoolchemistry.com/lessonplans/chapter2/lesson1 Accessed on March 20th 2018.
  • Isaac Physics, isaacphysics.org/concepts/cc_cooling_curves. Accessed on 17th September 2018.
  • Jones, Edward Charles Snell, and James Kenner. “CCXLVIII.-The Direct Formation of Quinones from 2 : 6-Disubstituted Derivatives of 4-Nitrophenol.” Journal of Materials Chemistry C, The Royal Society of Chemistry, 1 Jan. 1931, pubs.rsc.org/-/content/articlelanding/1931/jr/jr9310001842/unauth#!divAbstract. Accessed on April 19th 2018.
  • K.F.Gan, and A.H.W.Ngan. “Acta Materialia.” The Unusual Size Effect of Eutectic Sn/Pb Alloys in the Micro Regime: Experiments and Modeling, 1 June 2018, doi:https://doi.org/10.1016/j.actamat.2018.04.005. Accessed on September 11th 2018.
  • Liu Xue, et al. doi: doi:10.4028/www.scientific.net/AMM.519-520.1164. Accessed on- January 27th 2018.
  • Natural Disasters & Assessing Hazards and Risk, www.tulane.edu/~sanelson/eens211/2compphasdiag.html. Accessed on December 23rd 2018
  • “Naphthalene.” National Center for Biotechnology Information.PubChem Compound Database, U.S. National Library of Medicine, pubchem.ncbi.nlm.nih.gov/compound/naphthalene#section=Top. Accessed on 20th January 2019
  • “Naphthalene.” National Center for Biotechnology Information.PubChem Compound Database, U.S. National Library of Medicine, http://pubchem.ncbi.nlm.nih.gov/compound/naphthalene#section=Top. Accessed on 20th January 2019
  • “p-Nitrophenol.” National Center for Biotechnology Information.PubChem Compound Database, U.S. National Library of Medicine, pubchem.ncbi.nlm.nih.gov/compound/4-Nitrophenol#section=Top. Accessed on november 7th 2018.
  • “p-Nitrophenol.” National Center for Biotechnology Information. PubChem Compound Database, U.S. National Library of Medicine, pubchem.ncbi.nlm.nih.gov/compound/4-Nitrophenol. Accessed on November 7th 2018.
  • Reactions of the Group 2 Elements with Water, http://www.chemguide.co.uk/physical/phaseeqia/snpb.html. Accessed on 15th janurary 2019.
  • “Solvent Properties of Water.” Khan Academy, Khan Academy, http://www.khanacademy.org/science/biology/water-acids-and-bases/hydrogen-bonding-in water/a/water-as-a solvent. Accessed on June 18th 2018
  • Science.gov, http://www.science.gov/topicpages/n/naphthalene+sublimation+technique. Accessed on October 19th 2018.
  • “The Calculation of Eutectic Temperatures and Concentrations in Two- and Multi-Phase Systems.” Springer. Accessed on November 13th 2018
  • “The Calculation of Eutectic Temperatures and Concentrations in Two- and Multi-Phase Systems.” Springer.Accessed on November 13th 2018
  • Urvi Gala, et al. “Pharmaceutical Applications of Eutectic Mixtures.” Journal of Developing Drugs, doi:http://dx.doi.org/10.4172/2329-6631.1000e130. Accessed on February 11th 2019.
  • Willis H. Smith Jr., et al. “Molecular Crystals and Liquid Crystals .” Experimental Methods for Determining the Eutectic Composition of a Multi-Component Liquid Crystal Mixture, doi: https://doi.org/10.1080/00268949108033380. Accessed on December 20th 2018
  • “X-Ray Powder Diffraction (XRD).” Examples, 5 Mar. 2019, http://serc.carleton.edu/research_education/geochemsheets/techniques/XRD.html. Accessed on February 11th 2019.

Appendix-

Naphthalene

Naphthalene is a white, volatile, solid polycyclic hydrocarbon with a strong mothball odour. It is obtained from either coal tar or petroleum distillation and is primarily used to manufacture phthalic anhydride, but is also used in moth repellents. Its molecular formula is C10H8 with a molecular weight of 128.174 g/mol.

Figure 13 - Structural Formula Of Naphthalene
Figure 13 - Structural Formula Of Naphthalene

nitrophenol

4-Nitrophenol is a phenolic metabolite of environmental chemicals present in samples from the general population. Its measurement in urine is used in biological monitoring for establishing the presence and magnitude of exposures to pesticides. It has a molecular formula of C6H5NO3 and a molecular weight of 139.11 g/mol.

Figure 14 - Structural Formula Of 4-Nitrophenol
Figure 14 - Structural Formula Of 4-Nitrophenol
Figure 15 - Table on Materials required
Figure 15 - Table on Materials required
Apparatus
Capacity
Quantity
Least count
Uncertainty
Test-tube

10 cm3

1
-
-
Conical Flask

250cm3

1
-
-
Water Bath
-
1
-
-
Temperature Probe
-
1
-
±0.01°C
Spatula
-
1
-
-
Mass balance
0.01 - 600grams
1
-
±0.01 grams
Stopwatch
-
1
-
±0.01 seconds
Figure 16 - Table on Apparatus required

Safety precautions

  • Exposure to naphthalene is associated with hemolyticanemia, damage to the liver and neurological system, cataracts and https://pubchem.ncbi.nlm.nih.gov/compound/retinal hemorrhage. Naphthalene is reasonably anticipated to be a human carcinogen and may be associated with an increased risk of developing laryngeal and colorectal cancer.
  • Acute (short-term) inhalation or ingestion of 4-nitrophenol in humans causes headaches, drowsiness, nausea, and cyanosis (blue colour in lips, ears, and fingernails). Contact with eyes causes irritation in humans.
  • Safety precautions are of paramount importance.
  • Use chemical safety goggles and/or a full face shield where splashing is possible. Maintain eye wash fountain and quick-drench facilities in work area.
  • Wear impervious protective clothing, including boots, gloves, lab coat, apron or coveralls, as appropriate, to prevent skin contact.
  • Ensure adequate ventilation and keep away from ignition sources and static electricity. Prevent formation of dust. Dust can combine with air to form an explosive mixture. Use chemical resistant gloves, safety glasses and dust mask. Keep breathing equipment ready.
  • Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. Body Protection impervious clothing, The type of protective equipment must be selected according to the concentration and amount of the naphthalene and 4-nitrophenol.
  • Naphthalene is heated using a water bath and not directly using a Bunsen burner as it is a heat sensitive material and is flammable.

Procedure

  • Calibration of temperature probe

A laboratory thermometer is calibrated using a beaker with water and ice, the thermometer is added in the beaker with water and ice and checked if the temperature shown on the thermometer is 0 ±0.5 0C, to ensure there is no zero error in it.

  • Calibration of the mass balance

Known mass of 1 gram is put on the mass balance and checked if it shows the right reading for the mass (1.00 gram) to ensure mass balance is calibrated properly.

Raw data

Figure 17 - Table on Temperature Change With Time For 4 Grams Of Naphthalene And 1 Grams Of 4-Nitrophenol
Figure 17 - Table on Temperature Change With Time For 4 Grams Of Naphthalene And 1 Grams Of 4-Nitrophenol

Here,

 

The freezing temperature of the composition is = 58°C

 

Since at 38C the temperature is constant for a few minutes, which means that the composition is changing its physical state.

Figure 18 - Table On Temperature Change With Time For 3 Grams Of Naphthalene And 2 Grams Of 4-Nitrophenol.
Figure 18 - Table On Temperature Change With Time For 3 Grams Of Naphthalene And 2 Grams Of 4-Nitrophenol.

Here,

 

The freezing temperature of the composition is = 35°C

 

Since at 35°C the temperature is constant for a few minutes, which means that the composition is changing its physical state.

Figure 19 - Table On Temperature Change With Time For 2 Grams Of Naphthalene And 3 Grams Of 4-Nitrophenol
Figure 19 - Table On Temperature Change With Time For 2 Grams Of Naphthalene And 3 Grams Of 4-Nitrophenol

Here,

 

The freezing temperature of the composition is = 55°C

 

Since at 35°C the temperature is constant for a few minutes, which means that the composition is changing its physical state.

Figure 20 - Table on Temperature Change With Time For 1 Grams Of Naphthalene And 4 Grams Of 4-Nitrophenol
Figure 20 - Table on Temperature Change With Time For 1 Grams Of Naphthalene And 4 Grams Of 4-Nitrophenol

Here,

 

The freezing temperature of the composition is = 68°C

 

Since at 41°C the temperature is constant for a few minutes, which means that the composition is changing its physical state.

Figure 21 - Table on Temperature Change With Time For Ograms Of Naphthalene And 5 Grams of 4-Nitrophenol
Figure 21 - Table on Temperature Change With Time For Ograms Of Naphthalene And 5 Grams of 4-Nitrophenol

Here,

 

The freezing temperature of the composition is = 105°C

 

Since at 51C the temperature is constant for a few minutes, which means that the composition is changing its physical state.

Figure 22 - Variation Of Time (Seconds) Against Temperature Of Mixture Of 4 Grams of Naphthalene And 1 grams Of 4-Nitrophenol.
Figure 22 - Variation Of Time (Seconds) Against Temperature Of Mixture Of 4 Grams of Naphthalene And 1 grams Of 4-Nitrophenol.

In the graph it can be observed that the temperature stays constant at 58C for a few minutes showing that it is the freezing point.

Figure 23 - Variation Of Time (Seconds) Against Temperature Of Mixture Of 3 Grams Of Naphthalene And 2 Grams Of 4-Nitrophenol.
Figure 23 - Variation Of Time (Seconds) Against Temperature Of Mixture Of 3 Grams Of Naphthalene And 2 Grams Of 4-Nitrophenol.

In the graph it can be observed that the temperature stays constant at 35C for a few minutes showing that it is the freezing point.

Figure 24 - Variation Of Time (Seconds) Against Temperature Of Mixture of 2 Grams of Naphthalene And 3 Grams of 4-Nitrophenol.
Figure 24 - Variation Of Time (Seconds) Against Temperature Of Mixture of 2 Grams of Naphthalene And 3 Grams of 4-Nitrophenol.

In the graph it can be observed that the temperature stays constant at 55C for a few minutes showing that it is the freezing point.

Figure 25 - Variation Of Time (Seconds) Against Temperature Of Mixture Of 1 Grams Of Naphthalene And 4 Grams Of 4-Nitrophenol.
Figure 25 - Variation Of Time (Seconds) Against Temperature Of Mixture Of 1 Grams Of Naphthalene And 4 Grams Of 4-Nitrophenol.

In the graph it can be observed that the temperature stays constant at 68C for a few minutes showing that it is the freezing point.

Figure 26 - Variation Of Time (Seconds) Against Temperature Of Mixture Of 0 Grams Of Naphthalene And 5 Grams Of 4-Nitrophenol.
Figure 26 - Variation Of Time (Seconds) Against Temperature Of Mixture Of 0 Grams Of Naphthalene And 5 Grams Of 4-Nitrophenol.

In the graph it can be observed that the temperature stays constant at 105C for a few minutes showing that it is the freezing point.

Find the freezing point of a 4g naphthalene and 1g 4-nitrophenol mixture.

Mass of naphthalene = 4 g = 0.004 kg

 

Mass of 4-nitrophenol = 1 g

 

Number of moles of 4-nitrophenol = \(\frac{1}{139.11}\) = 0.007

 

Molality of the solution (m) = \(\frac{moles\ of\ solute (4-nitrophenol)}{mass\ of solvent (napthalene\ ) in \ kg}=\frac{0.007}{0.004}\) = 1.75

 

Cyroscopic constant (Kf) for naphthalene =7.01

 

Depression of freezing point (∆Tf) = Kf.m = 7.01X 1.75 = 12.26

 

Freezing point of the mixture (Tf) = Freezing point of pure naphthalene - ∆Tf = 80.2 – 12.26 = 67.9C

;