EXPERIMENT: SOLUBILITY CURVES Objectives The objectives of this experiment are; To calculate the solubility of a substance under a variety

ty of temperatures. To construct solubility curves based on experimental data.

Introduction Crystals A crystal may be defined as a solid composed of atoms arranged in an orderly, repetitive array. The inter-atomic distances in a crystal of any definite material are constant and are characteristic of that material. Because the pattern or arrangement of the atoms is repeated in all directions, there are definite restrictions on the kinds of symmetry that crystals can possess. There are five main types of crystals, and these types have been arranged into seven crystallographic systems based on the crystal interfacial angles and the relative length of its axes. The treatment of the description and arrangement of the atomic structure of crystals is the science of crystallography. Crystallisation, one of the oldest of unit operations, is used to produce vast quantities of materials, including sodium chloride, sodium and aluminium sulphates and sucrose. Many organic liquids are purified by crystallisation rather than by distillation since enthalpies of crystallisation are generally much lower than enthalpies of vaporisation and crystallisation may be carried out closer to ambient temperature thereby reducing energy requirements. Against this, crystallisation is rarely the last stage in a process and solvent separation, washing and drying stages are usually required. Crystallisation is also a key operation in the freeze-concentration of fruit juices, the desalination of sea water, the recovery of valuable materials such as metal salts from electroplating processes, the production of materials for the electronic industries and in biotechnological operations such as the processing of proteins. To produce crystals it is best to start with a saturated solution. A more dilute solution will become saturated as the air evaporates some liquid, but natural evaporation takes time. Crystals can be obtained more quickly if the solution is saturated to begin with. A saturated solution can be made by adding solute to the solvent. Starring to mix would help to dissolve the solute. Heat may be applied to help dissolve the solute.

Solubility and Phase Diagrams Equilibrium relations for crystallization systems are expressed in the form of solubility data which are plotted as phase diagrams or solubility curves. Solubility data are ordinarily given as parts by weight of anhydrous material per 100 parts by weight of total solvent. In some cases these data are reported as parts by weight of anhydrous material per 100 parts of solution. If water of crystallization is present in the crystals, this is indicated as a separate phase. The concentration is normally plotted as a function of temperature and has no general shape or slope. It can also be reported as a function of pressure, but for most materials the change in solubility with change in pressure is very small. If there are two components in solution, it is common to plot the concentration of these two components on the X and Y axes and represent the solubility by isotherms. Solubility curves, like the one shown in figure 1 below gives an indication of what mass of solute would dissolve in 100g of water over a range of temperatures.

Fig. 1 solubility curves for KNO3, NaCl and MnSO4.H2O at different temperatures

When three or more components are present, there are various techniques for depicting the solubility and phase relations in both three dimensions and two-dimension models.

A key factor affecting the solubility of any substance (i.e. how much solute can be dissolved in a solvent) is temperature. For most substance increasing temperature will increase solubility- more solute will be able to dissolve in the same of solvent. A solubility curve illustrates how the solubility of a substance varies with temperature. By determining the mass of solute that can dissolve in a volume of solvent under a variety of temperatures we can easily construct a solubility curve. Safety Caution was emphasised when using water bath to avoid burns and splashes to the eyes. Equipment and materials The following were used during the experiment; Sodium chloride, sodium nitrite and potassium nitrate. Distilled water Test-tube Water baths Test-tube clamp Thermometers Spatula Test-tube labels Pen/pencil Distilled water Measuring cylinder

Procedure 1. A water bath was prepared by filling a large beaker approximately 2/3 full with water. The beaker was placed on the tripod stand above the Bunsen burner and the water was heated to just below boiling. Water was left to heat. 2. 3. The test tubes were labelled and numbered 1 to 4. The following masses of sodium chloride salt were measured accurately and placed in the appropriate test tube: a) Test tube 1: 2 grams NaCl b) Test tube 2: 4 grams c) Test tube 3: 6 grams d) Test tube 4: 8 grams

4. 5.

Exactly 5.0 mL of water was added to each of the test tubes. Each of the tube was placed into the water bath in order to dissolve the NaCl in each test tube. A stirring rod was used to help the dissolving process.

6.

Test tube 1 was removed from the water bath once the NaCl has fully dissolved and a thermometer was placed in the tube. The temperature at which crystals started forming within the test tube was recorded.

7. 8.

Step 6 was repeated for the other test tubes once NaCl dissolved. Steps 2 to 7 were repeated for NaNO2 and KNO3.

Results The following data was obtained and the mass volume ratio for each test-tube used was converted into mass/100 mL ratio. Also temperature at which crystallization occurred was obtained. A) Sodium chloride

Test tube 1 2 3 4

Mass NaCl (g) used 2 4 6 8

Volume water (mL) 5 5 5 5

Convert to g/100 mL 40 80 120 160

Saturation temp (oC) 62 78 85 90

B)

Sodium nitrite

Test tube 1 2 3 4

Mass NaNO2 (g) used 2 4 6 8

Volume water (mL) 5 5 5 5

Convert to g/100 mL 40 80 120 160

Saturation temp (oC) 7 42 58 68

C)

Potassium nitrate Mass KNO3 (g) used 2 4 6 8 Volume water (mL) 5 5 5 5 Convert to g/100 mL 40 80 120 160 Saturation temp (oC) 30 45 60 80

Test tube 1 2 3 4

A curve of concentration (g/100 mL) against temperature was plotted to obtain the solubility curves of sodium chloride, sodium nitrite and potassium nitrate as shown bolw

CURVE OF CONCENTRATION AGAINST TEMPERATURE

180

160
NaNO2

140

Concentration (solute g/100g H2O)

120

KNO3 NaCl

100

80

60

40

20

0 0 10 20 30 40 50 60 70 80 90 100

Temperature

(oC)

Discussion and tasks 1. The solubility curves for NaNO2 and KNO3 depict almost similar correlations for the experimental data as compared to the one given in literature except for the solubility curve of NaCl. The curve should not be steep as indicated in the results of the experiment. The possible reasons for this difference can be due to inaccuracy when reading the temperature when crystals formed. NaCl also has a low temperature coefficient of solubility and crystals do not form easily hence the need for some of the solvent to be evaporated for proper crystallization to take place. The need for evaporation of some of the solvent was not included in the procedure hence poor results for NaCl salt. 2. Based on the solubility curves obtained the following are the solubilitys of the salts at different temperatures: a) NaCl at 0 oC 2g/100mL water At 50 oC 28g/100mL water At 70 oC 58g/100mL water At 100 oC 220g/100mL water b) NaNO2 at 0 oC 36g/100mL water At 50 oC 96g/100mL water At 70 oC 164g/100mL water At 100 oC 260g/100mL water c) KNO3 at 0 oC 8g/100mL water At 50 oC 92g/100mL water At 70 oC 140g/100mL water At 100 oC 188g/100mL water 3. Based on the solubility curves obtained the following solutions can be described as; (a) 70g/100mL water at 45 oC (supersaturated for NaCl, unsaturated for KNO3 and unsaturated for NaNO2) (b) 80g/100mL water at 70 oC (supersaturated for NaCl, unsaturated for KNO3 and unsaturated for NaNO2) (c) 80g/100mL water at 30 oC (supersaturated for NaCl, supersaturated for KNO3 and supersaturated for NaNO2 ) 4. A successful industrial crystallization typically requires the development of a robust process in the laboratory. Knowledge of the solubility curve and the stability of the solution in the vicinity of the equilibrium point are essential to the successful development, optimisation, and scale-up of a crystallization process. The solubility curve is essential for the design of a crystallization process

as it helps indicate yield, the type of crystallization process to perform, and the rate of supersaturation generation. The solubility curve is typically constant for a given solute/solvent system (assuming impurity levels are not changing). Recommendations Rather than simply fitting a curve to the solubility data, using some of the solubility correlations available in the literature is recommended. These should yield success when extrapolating the solubility curve over a wide range. However, it is recommended that the Solubility curve be measured over the desired operating range to help avoid potential errors that are associated with extrapolation of solubility curves (this is evident when the task involved reading solubility of the different salts at different temperatures that required extrapolation). It is also recommended that during crystallization of sodium chloride some of the solvent be evaporated so as to ease the process of crystallization as NaCl has a low temperature coefficient of solubility. Conclusion The technique for experimentally measuring the solubility curve is relatively straightforward. It should allow the quick and efficient evaluation of many solvents and assess their impact on both the solubility curve and meta-stable behaviour of the solution. However, to fully evaluate the behaviour of a solute in a given solvent, a variety of additional experiments should be performed. It is reported that solution history can have an impact on the point of nucleation. Experimental solubility results for KNO3, NaNO2 and NaCl and water systems agree fairly well with literature values. It can also assess future scalability of process: Impact of solids, solution history, and mixing.

Reference 1. Albrights Chemical Engineering handbook. 2. Lab manual by Dennis O Otieno 3. Coulson and Richardson, Chemical Engineering Volume II 4. McCabe, Smith and Harriot, Unit operations in chemical engineering 5. http://galileo.phys.virginia.edu/ 6. www.wikipedia.com 7. http://web.mit.edu/physics/