ADAMSON UNIVERSITY College of Engineering Chemical Engineering Department

M a n il a

Physical Chemistry for Engineers 2 Laboratory Manual

Prepared by: Committee for Laboratory Manual of the Chemical Engineering Department

Table of Contents: Course Description Policies and Guidelines on the use of ChE/Chem Laboratories Instruction for Preparing Laboratory Reports (i) (ii) (iii)

Experiment No. 1 2 3 4 5 6 7 8 9 10

Title

Distillation of Binary Liquids Steam Distillation Solubility Diagram of a Partially Miscible Liquid System Distribution Phase Diagram of a Three Component Liquid System Adsorption Chemical Equilibrium Chemical Kinetics Galvanic Cells Conductimetry

COURSE SYLLABUS IN PHYSICAL CHEMISTRY FOR ENGINEERS -2 (Laboratory) Course Description: This laboratory course accompanying Physical Chemistry 2 (lecture) is a continuation of Physical Chemistry 1 laboratory which covers the experiments on chemical equilibria, phase equilibria, surface phenomena, thermochemistry, kinetics and electrochemistry. No. of hours Course Credit Units Course Objectives: After completing this course, the students must be able to: 1. Develop sound judgement in interpreting and correlating experimental data based on the principles learned in Physical Chemistry. 2. Develop initiative, resourcefulness, and leadership by demonstrating full responsibility in performing the experiments assigned. 3. Acquire laboratory skills by following accepted laboratory handling and waste disposal techniques. 4. Develop safety consciousness by observing proper laboratory techniques at all times while working in the laboratory. : : 3 hours per week 1 unit

POLICIES AND GUIDELINES ON THE USE OF CHEMICAL ENGINEERING/CHEMISTRY LABORATORIES 1. Chemical Engineering laboratories are open for equipment review and other preparatory work from 8 am to 5 pm Monday through Friday. Equipment may only be operated and chemicals will be dispensed during scheduled laboratory hours. Written approval of the faculty adviser, laboratory coordinator, and ChE chairperson are required for anyone (e.g. research students) to use the laboratory during Saturdays or to operate equipment on non-scheduled laboratory days. 2. For the use of equipment, computers, and chemicals, students and faculty members must sign in the log books for proper monitoring of the equipment. 3. No equipment is to be operated until the approval of the instructor and laboratory coordinator has been obtained at the check-in meeting. Only the equipment pertaining to the assigned experiment is to be operated. All members of a group are to be properly informed on the safety aspects of their assigned experiment and to be familiar with the safety aspects of surrounding experiments. Before any apparatus can be operated in the laboratory, the group must have a second on-site safety check-in. 4. Students are required to prepare handling and storage procedures of chemicals and materials to be used and waste disposal/treatment procedures approved by the faculty adviser and laboratory coordinator prior to any experiment. 5. Transfer or movement of equipment or devices from the laboratories will not be allowed without approval of advance notice (at least 2 days before the request schedule) from the laboratory coordinator. 6. In borrowing glassware and accessories of the equipment, equipment and in using laboratory facility, students must accomplish Form A (Request for the Use of Laboratory Facilities and Equipment) with the signature of the professor. 7. In case of breakages, damages, or losses: (A) A student accomplishes three copies of the Breakage Forms/Charge Slip Form ( Form B) duty signed by all members of the group. (B) The student requests the signature of the instructor and returns the form to the laboratory personnel. (C) The laboratory personnel indicate the price of the damaged or lost item. (D) The students are given one week to replace the items with the same brand or specifications. If the students fail to replace the said item, the item is then forwarded to the Cashiers Office for payment. (E) After payment, the students return the forms to the laboratory personnel with the photocopy of the official receipt. (F) They must be advised to keep the original receipt for future reference. 8. Students should always wear their laboratory gowns or aprons when working in the laboratory. Safety goggles and safety gloves must also be worn whenever applicable. Students must also observe proper attire specifically closed footwear to protect them from spilled chemicals or hot fluids. Neckties, dangling clothing or jewelry and other unsafe items are prohibited.

9. Sleeping is prohibited in the laboratory. Violation of this rule will result in dismissal from the laboratory for that day. 10. Horseplay of any sort is absolutely prohibited in the laboratory. 11. As a general rule, eating, drinking, chewing gum, and smoking are not allowed inside laboratories. 12. All safety precautions must be followed at all times. 13. No operating equipment will be left unattended. At least two members of the group must be present while the equipment is operating. 14. The laboratory floor must be kept dry, clean, and uncluttered at all times. Any spills should be cleaned up immediately. 15. All injuries, accident, hazardous situation, losses, leaks, malfunctions or breakages must be reported to the laboratory personnel or professor immediately. 16. All chemicals must be transported in a safety carrier. All mercury and alcohol thermometers and more than one item of glassware must be transported in a bucket or other suitable container. 17. The students are expected to be familiar with the safety aspects of all chemicals used in the laboratory. 18. Listening to radios, walkman, MP3s, MP4s, etc. is strictly prohibited in the laboratory. 19. Playing computer games; using and recharging of cellular phones; or viewing DVDs is prohibited in the laboratory. 20. Applying cosmetics are prohibited in the laboratory. 21. Precautions should be taken to prevent long hair from being entangled in moving parts of the equipment. 22. A violation notice will be issued by the Laboratory Coordinator or Laboratory Student Assistant or by the assigned Laboratory Professor to any student found violating any of these rules and regulations. 23. Any SERIOUS VIOLATION of any of these safety rules or laboratory policies may lead to immediate dismissal from the laboratory. A person who repeatedly disregards the safety rules or laboratory policies for at least 3 times will be called in for disciplinary action with the ChE chairperson. A penalty that suits the violation may be imposed and, at the discretion of his/her laboratory professor, the students grade may be severely affected. Other policies may be given as situation arises and in consideration of our best interest. It is expected that these sets of policies serve as a guide for us to work safely and efficiently.

Instructions for Preparing Laboratory Reports The report must be prepared and will be graded according to the following outline: Subject 1. Title page 2. Abstract 3. Introduction 4. Theoretical Background 5. Procedure 6. Results 7. Discussion of Results 8. Conclusions and Recommendations 9. Literature Cited 10 Nomenclature Appendices A1 Raw Data A2 Analysis of data & Sample Calculation Organization & neatness Total: 1. Title Page The Title page should be separate from the rest of the report. It should contain: a. The name of the experiment b. The number of course c. The date when the experiment was run d. The name of the writer and his co-workers, ID number, and his group number e. The name of the instructor to whom the report is submitted f. The date of submission of report 5 20 5 100 Marks 2 12 3 5 4 8 24 8 2 2

2. Abstract The abstract should be informative, and should be written in about three to five sentences. It should cover all phases of the investigation. It must include the following: a. An introductory statement about the subject matter b. Briefly describe what was done. c. Present some selected result (numerical values, if possible). d. If possible, present some percentage errors in experimental results in comparison with theoretical values. While writing the abstract, it should be kept in mind that you should not refer to any graph or table. 3. Introduction This section should include few sentences discussing the physical and/or chemical principles involved in the experiment. 4. Theoretical Background This section should include the theory behind the experiment. It should also contain all those equations, which are used to acquire a certain result. Theoretical correlations, which are used for comparison with experimental results, should also be included. 5. Procedure Here, you should briefly describe the actual step-by-step procedure you followed in running the experiment. It should be written in your own words, e.g. the needle valve was manipulated in order to adjust the liquid flow rate. 6. Results The results should be presented in the form or Tables or graphs. The Table should contain the results obtain from experiments and from theoretical knowledge. Comparisons should be presented in terms, e.g. percent deviation. 7. Discussion of Results In this section you should discuss you experimental results. Show how you make comparison with the values obtained theoretically. Also discuss the deviation of experimental results from theoretical values. The possible source of errors should also be mentioned. If the results are obtained in terms of graphs, then interpret them also. 8. Conclusions and Recommendations Conclusions are the series of numbered sentences which answer the questions posed in the end of each experiments. Conclusions should also include the errors between the experimental and theoretical values. What you have learned from the experiment should be mentioned as well. Recommendations are the proposals for future work, e.g. suggested changes in equipment, study of new variables, or possible experiments in relative fields. Like the conclusions, the recommendations are usually listed by numbers, and each consists of only a sentence or two. 9. Literature Cited

Here, you should list the books, Journals articles, etc. used in writing your report and analyzing the experiment. The reference should be completed (name of the book, author, volume, date of publication, pages, etc.). References should be arranged alphabetically by author. 10. Nomenclature The symbols, which are used in the report, should be defined in the nomenclature in alphabetical order. The accompanying definitions must include proper units. Appendices All appendices and graphs should be attached at the end of the report. A1. Raw Data: It should contain the data on which the experiment was done. A2. Analysis of Data and Sample Calculations: This shows how the data/manipulated data is transformed into experimental results by using the appropriate equations. Also, how the theoretical results are obtained using theoretical in terms of percentage error. Sample calculations should contain each step, which is used to acquire certain results.

Experiment 1 DISTILLATION OF BINARY LIQUIDS OBJECTIVE: To construct a boiling point-composition diagram for a binary liquid system. DISCUSSION: When a mixture of two liquids is distilled, the boiling point will be that temperature at which the sum the sum of the partial vapour pressures of the two liquids is equal to the atmospheric pressures. If the liquids form an ideal solution, then the partial pressures can be calculated with the aid of Raoults law and the total pressure can be expresses by the equation P=N1p1+ N2p2, where P is the total pressure, N1 and N2 are the more fractions of compounds 1 and 2, respectively, and p1 and p2 are the vapour pressures that the pure compounds 1 and 2, respectively, would have at the given temperature. If the attractive forces between unlike molecules are greater than between like molecules, then the total pressure will be less than that predicted by Raoults law; if the attractive forces between unlike molecules are less than between like molecules, then the total pressure will be greater than that predicted by Raoults law. A lower total pressure corresponds to a higher boiling point, and vice versa. A boiling point composition diagram consists of two curves on the same graph. (1) a plot of the composition (usually mole fraction) of a liquid against its boiling point, (2) a plot of the composition of the vapour in equilibrium with the liquid at its boiling point. MATERIALS: 250-ml distilling flask, condenser, adaptor, thermometer, 1225-ml Erlenmeyer flasks, 10-ml graduated cylinder, 5-ml pipets, 100-ml beaker, 600-ml beaker, burette, iron stand, burette clamp, boiling chips, glacial acetic acid, 1M NaOH, phenolphthalein indicator. PROCEDURE: 1. Prepare a simple distillation set-up. 2. Mix 50-ml of glacial acetic acid and 1-ml of distilled water in a 100-ml beaker. 3. Pipet 1 ml of the mixture into each of two 125-ml Erlenmeyer flask and label both flasks L-1 to make two trials. 4. Transfer the rest of the solution in step 2 to the distilling flask in the set-up and add the boiling chips. 5. Slowly distill the mixture collecting the distillate in a clean, dry 10-ml graduated cylinder. Read and record the temperature when 3-ml of the distillate has been collected. Stop the distillation when 6-ml of the distillate has been collected.

6. Pipet 1-ml of the solution remaining in the distilling flask into each of the Erlenmeyer flasks previously labelled L-1 in step 3. 7. Pipet 2-ml of the distillate from step 5 into each of the two Erlenmeyer flasks and label both flasks V-1. 8. Add 5-ml of distilled water to the remaining solution in the distilling flask. Distill over 1-2 ml to wash out the condenser. 9. Stop heating and pipet 1-ml of the solution into each of two 125-ml Erlenmeyer flasks labelled L-2. 10. Repeat steps 5 to 7 labelling the distillate fractions as V-2. 11. Repeat steps 8-10 using 10, 20, and 30 ml of distilled water labelling the flasks L-3 and V-3, L-4 and V-4, and L-5 and V-5, respectively. 12. Titrate the solutions in the flasks with 1 M NaOH using phenolphthalein as indicator. 13. Record the data on the report sheet and calculate the mole% of acetic acid in the solutions. Assume that the density of all solutions is 1.05g/ml. 14. Construct the boiling point-composition diagram of the binary liquid system acetic acid-water by plotting boiling point against composition in mole% acetic acid.

Experiment No. 1
DISTILLATION OF BINARY LIQUIDS

PRELAB EXERCISES NAME: __________________________________________ PROFFESOR: ______________________________________ DATE: _________________ SCORE: ________________

1. At 90C, the vapour pressure of methylbenzene is 400 Torr and that of 1,2-dimethylbenzene is 150 Torr. What is the composition of a liquid mixture that boils at 90C when the pressure is 0.50 atm? What is the composition of the vapour produced?

2. The vapour pressure of pure liquid A at 300 K is 575 Torr and that of pure liquid is 390 Torr. These two compounds form an ideal liquid and gaseous mixtures. Consider the equilibrium composition of a mixture in which the mole fraction of A in the vapour is 0.350. Calculate the total pressure of the vapour and the composition of the liquid mixture.

3. It is found that the boiling point of a binary solution of A and B with x A=0.6589 is 88C. At this temperature the vapor pressures of pure A and B are 957.0 Torr and 379.5 Torr, respectively. (a) Is this solution ideal? (b) What is the initial composition of the vapour above the solution.

Experiment No.1
DISTILLATION OF BINARY LIQUIDS PRELIMINARY DATA SHEET: Date: _______________ Group No.: ___________ SIGNATURE Leader: Members: ____________________________________ ____________________________________ ____________________________________ _______________________________________ __________________________ ____________________________ __________________________ ____________________________ Score: _______

THEORETICAL FRAMEWORK: (PREPARE A FLOWCHART OF THE PROCEDURE OF THE EXPERIMENT) EXPERIMENTAL RESULTS AND OBSERVATIONS: Trial Boiling Point 1 L ml of NaOH 2 1 V 1 1 L Mole % HC2H3O2 2 1 2 V L Ave. V

Run No. 1 2 3 4 5

Concentration of NaOH solution Boiling Point of HC2H3O2 Boiling Point of H2O

_____________________ M _____________________ _____________________

Boiling Point Composition Diagram of the System HC2H3O2-H2O

Sample Computation:

Approved by: _______________________ PROFESSOR

GUIDE QUESTIONS AND PROBLEMS:

1. How do attractive forces between like molecules compare with attractive forces between unlike molecules in the system acid-water? Support your answer.

2. How do you expect the composition of the vapour above the solution of a mixture of acetic acid and water to compare with that of the liquid with which it is in equilibrium?

3. Define an Azeotrope. Does the system form an azeotrope mixture? Explain your answer.

Experiment No. 2 STEAM DISTILLATION OBJECTIVE: To study the process of steam distillation. DISCUSSION: When, in a mixture of two liquids, the attraction between like molecules is greater than that between unlike molecules, the total vapour pressure is greater than that predicted by Raoults law. As this difference in attraction increases, a point will be reached where the two liquids will no longer miscible in all proportions; further increase will decrease the range of miscibility until, as a limiting case, the liquids can be considered to be completely immiscible in each other. The total vapour pressure over these systems will differ more and more from that predicted by Raoults law until, in the limiting case mentioned above, the vapour pressure will be equal to the sum of the vapour pressures of the two pure liquids at the same temperature and will be independent of the mole fraction of each liquid present. In this limiting case, the ratio of the partial pressures of the compounds in the vapour will be equal to the ratio of the vapour pressures of the pure compounds, at a temperature equal to the boiling point of the mixture. Thus,

=
and

where pA and pB are the vapour pressures of the pure compounds, p A and pB are the partial pressures of the compounds in the vapour, P is the total pressure, N A and NB are the mole fractions of the compounds in the vapour (or distillate)m nA and nB are the moles of the compounds in the vapour (or distillate), w A and wB are the weights of the compounds in the vapour (or distillate), and M A and MB are the molecular weights of the compounds. Steam distillation is found to be a useful method of distilling a liquid which is immiscible with water, has an appreciable vapour pressure between 80 and 100C., and would decompose if distilled directly from the mixture at the higher temperature required. Although toluene does not decompose, it fulfils the other requirements and will be used here because of experimental convenience.

MATERIALS: 250-mL distilling flask, 1-L round-bottom flask, condenser, thermometer, glass tubing, 50-mL graduated cylinder, adapter, toluene 1. Prepare a steam distillation set-up as in the figure below. Have the set-up approved by your instructor before proceeding with the experiment.

source: http://www.chembook.co.uk/chap23.htm

2. Place 50-mL of toluene in the distilling flask. Heat the steam generator using a large flame. When the water starts boiling lower the flame to a size just enough to continue boiling the water. 3. Discard the first 2-3 mL of distillate. Record the temperature before placing the receiver (50-mL graduated cylinder) under the adapter. 4. Continue the distillation and record the temperature when the total volume of distillate in the receiver has reached 5mL, 10mL, 15mL, 20mL, 25mL, 30mL, 35mL, 40mL, 45mL and 50 mL. Stop the distillation when 50mL of distillate has been collected. 5. Cool the distillate and allow the layers to separate completely. Read and record the volumes of the layers obtained. 6. From a handbook, secure data for the vapor pressure of toluene and water at 40C, 50C, 60C, 70C, 80C, 90C. Determine the vapor pressure of the mixture at given temperatures and plot the vapor pressures of toluene, water and the mixture on the same graphing paper. 7. From the graph obtained in step 6, determine the theoretical boiling point of the mixture. 8. Determine the theoretical composition of the distillate in mole % toluene and weight % toluene using the graph obtained from the previous step. Experiment No. 2
STEAM DISTILLATON

PRELAB EXERCISES NAME: __________________________________________ PROFFESOR: ______________________________________ DATE: _________________ SCORE: ________________

1. Benzene and toluene from nearly ideal solutions. At 20C the vapour pressures of pure benzene and toluene are 74 Torr and 22 Torr, respectively. The solution is boiled by reducing the external pressure below the vapour pressure. Calculate (a) the pressure when boiling begins, (b) the composition of each component in the vapour, and (c) the vapour pressure when only a few drops of liquid remains. Assume that the rate of vaporization is low enough for the temperature to remain constant at 20C.

2. The following temperature/composition data were obtained for a mixture of two liquids A and B at 1.00 atm, where x is the mole fraction in the liquid and y is the mole fraction in the vapour at equilibrium: /C xA yA 125 0.91 0.99 130 0.65 0.91 135 0.45 0.77 140 0.30 0.61 145 0.18 0.45 150 0.098 0.25

The boiling points are 124C for A and 155C for B. Plot the temperature/composition diagram for the mixture. What is the composition of the vapour in equilibrium with the liquid of the composition (a) xA=0.50 and (b) xB=0.33?

Experiment No. 2 STEAM DISTILLATION PRELIMINARY DATA SHEET

Date: _______________ Group No.: ___________ SIGNATURE Leader: Members: ____________________________________ ____________________________________ ____________________________________ ____________________________________ __________________________ ___________________________ __________________________ __________________________ Score: _______

THEORETICAL FRAMEWORK: (PREPARE A FLOWCHART OF THE PROCEDURE OF THE EXPERIMENT) EXPERIMENTAL RESULTS AND OBSERVATION:

Volume of distillate 0 mL 5 mL 10 mL 15 mL 20 mL 25 mL 30 mL 35 mL 40 mL 45 mL 50 mL

Boiling Point _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____

Temperature (

40 _____ _____

50 _____ _____ _____

60

70

80

90

Vapor pressure of water (Torr) Vapor pressure of toluene (Torr)

______ ______ ______ _____ ______ ______ ______ _____ ______ ______ ______ _____

Vapor pressure of the mixture (Torr) _____

Plot of P vs. T for Toluene, Water and the Mixture

Experimental boiling point of the mixture Theoretical boiling point of the mixture % Error Volume of toluene in distillate Volume of water in distillate Temperature of distillate Density of water (from handbook) Density of toluene (from handbook) Weight of water in distillate Weight of toluene in distillate Moles of water in distillate Moles of toluene in distillate Experimental composition of distillate

________ ________ ________ _______mL _______mL _________ ______g/mL ______g/mL ________g ________g _______moles _______moles _____mole % water

_____mole % toluene _____wt % water _____wt % toluene Theoretical composition of distillate _____mole % water _____mole % toluene _____wt % water _____wt % toluene % Error _____%

SAMPLE COMPUTATIONS:

Approved by: _______________________ PROFFESOR

GUIDE QUESTIONS AND PROBLEMS:

1. Give the advantages of using steam distillation in the recovery of an inorganic liquid from a mixture.

2. Is it possible to carry out steam distillation at a temperature higher than 100C at 1 atm? Why?

Experiment No. 3 SOLUBILITY DIAGRAM OF A PARTIALLY MISCIBLE LIQUID SYSTEM OBJECTIVE: To be able to prepare the solubility diagram of a partially miscible liquid system. DISCUSSION: In most cases, partially miscible liquids become more soluble in each other with increasing temperature until the critical solution temperature is reached, above which there is complete miscibility. In this experiment mixtures of known composition are heated until they dissolve completely. This is easily recognized by the disappearance of cloudiness due to two phases. A plot of composition vs. temperature shows the critical solution temperature. The phenol-water system readily gives satisfactory data. Since pure phenol is solid at room temperature and is messy to handle, an 80 percent by weight solution is used. This is dispensed from a burette, and

the weight is calculated from the volume and the density. Any solution of phenol is dangerous, so be careful. Avoid spilling and clean up immediately with large amounts of water. Never pipette by mouth. MATERIALS: 50-mL test tube, acid buret, iron stand, buret clamp, copper wire stirrer, thermometer, 600-mL beaker, tripod, burner, melted phenol PROCEDURE: 1. Prepare 80% phenol solution as follows: a. Weigh a clean and dry 100-mL graduated cylinder. b. Place about 20-mL of melted phenol in the cylinder and weigh. Record the weight of the phenol. c. By means of a buret, add distilled water equivalent to the weight of the phenol in the cylinder. (CAUTION: Phenol is corrosive. Avoid contact with your skin.)

2. Transfer all the phenol solution to a clean acid buret. 3. Deliver 10 mL of the phenol in the buret into a 50-mL test tube. Cover with a cork fitted with a thermometer and a copper wire stirrer. 4. By means of another buret, add distilled water to the phenol solution stirring continuously ring addition until the solution turns cloudy. Record the volume of the phenol solution. 5. Immerse the tube in a water bath (use a 600-mL beaker), then heat the water in the bath until the solution turns clear. Note the clearing temperature. (NOTE: The solution in the tube must be continuously stirred while doing this step.) 6. Remove the tube from the water bath and continuously stir the solution until the solution turns cloudy. Record the clouding temperature. 7. Deliver an additional 1.0 mL of water from the buret then repeat steps 5 and 6. 8. Repeat step 7 four (4) times. 9. Deliver 10.0 mL of distilled water from a buret into another ignition tube.

10. To the distilled water in the tube, add phenol solution from a buret while stirring constantly until the solution turns cloudy. 11. Treat the solution in the tube as in steps 5-8. 12. Record all data in the table. 13. Calculate the % by weight of pure phenol in all solutions obtained. The density of the 80% phenol solution is 1.05 g/mL.

Experiment No. 3 SOLUBILITY DIAGRAM OF A PARTIALLY MISCIBLE LIQUID SYSTEM PRELAB EXERCISES NAME: __________________________________________ PROFFESOR: ______________________________________ DATE: _________________ SCORE: ________________

The figure below shows the phase diagram for two partially miscible liquids, which can be taken to be that for water (A) and 2-methyl-1-propanol (B). Describe what will be observed when a mixture of

composition x_b=0.8 is heated, at each stage giving the number, composition, and relative amounts of the phases present.

Temperature, T 0

T1

0.2

0.4

0.6

0.8

Experiment No. 3 SOLUBILITY DIAGRAM OF A PARTIALLY MISCIBLE LIQUID SYSTEM PRELIMINARY DATA SHEET
Date: _______________ Group No.: __________ SIGNATURE Leader: ____________________________________ __________________________ Score: _______

Members:

____________________________________ ____________________________________ ____________________________________

__________________________ __________________________ __________________________

THEORETICAL FRAMEWORK: (PREPARE A FLOWCHART OF THE PROCEDURE OF THE EXPERIMENT) EXPERIMENTAL RESULTS AND OBSERVATION: A. Water Add to Phenol Run No. Clearing temperature (oC) Clouding temperature (oC) Average temperature (oC) Volume of phenol solution Weight of the phenol solution (W1) Weight of pure phenol Weight of water added to phenol (W2) Total weight of solution (WT) Weight % phenol 1 2 3 4 5 6

B. Phenol Added to Water Run No. Clearing temperature (oC) Clouding temperature (oC) Average temperature (oC) Volume of phenol solution Weight of phenol solution (W1) 1 2 3 4 5 6

Weight of pure phenol Weight of water added to phenol (W2) Total weight of solution (WT) Weight % phenol

COMPUTATIONS FOR A AND B:

Experiment No. 4 DISTRIBUTION OBJECTIVE: To determine the values of K and n in the distribution of acetic acid between water and diethyl ether. DISCUSSION: When a solute is added to a mixture of two miscible liquids and the system allowed to come to equilibrium at some given temperature, the following relationship will hold regardless of the quantity of solute added:

Ka= where Ka is the distribution constant, a1 and a2 are the activities of the solute in the two solvents, and n is the ratio of the average molecular weight in solvent 1 to its average molecular weight in solvent 2. Association will increase the average molecular weight, while dissociation will decrease it. It is to be noted that n may vary considerably with concentration due to changes in the degrees of association and dissociation. In order to simplify this experiment, concentrations will be substituted for activities in the above equation, so that the distribution equation becomes Kc= In this equation Kc may vary appreciably due to the change in activity coefficients with concentration. If, for any distribution system, the values of C 1 and C2 are obtained for two different total solute concentrations, both n and K can be calculated by solving the two equations for the two unknowns. In carrying out these calculations it may be convenient to take the logarithm of both sides of the above equation. The values of K and n obtained will be the average values for the two different concentrations in the calculations. MATERIALS: Glacial acetic acid, NaOH pellets, distilled water, phenolphthalein, Erlenmeyer flasks, base burette, iron stand, burette clamp, separatory funnel, iron ring, pipettes.

PROCEDURE: 1. Prepare by serial dilution 60 mL of each of the following starting from glacial acetic acid: 1.0 M, 0.50 M, and 0.25 M. (NOTE: to prepare solutions by serial distillation, prepare 120 mL of the 1.0 M solution from glacial acetic acid which is 17 M. Next, prepare 120mL of the solution from the 1.0 M solution. Finally, prepare 120 mL of the 0.25 M solution from 0.50 M solution.) Calculate the volumes of the acetic acid solution and water needed to prepare the desired solution. ) Prepare from NaOH pellets 0.50 M NaOH solution then prepare by distillation 200mL of 0.10 M NaOH solution.

2.

3. Pipet 25mL of the 1.0 M solution into a separatory funnel. Add 25mL of diethyl ether shake well and let stand for 10 minutes or until the layers are completely separated. 4. Draw the aqueous layer into a clean container then pipet 5.0mL into a clean 125-mL Erlenmeyer flask. Add 10mL of distilled water then titrate with 0.50 M NaOH to the phenolphthalein endpoint. Make 2 trials. 5. Pipet 10mL of the ether layer into 125-mL Erlenmeyer flask and add 10mL of distilled water. Titrate with 0.10 M NaOH to the phenolphthalein end point. Make 2 trials. 6. Repeat steps 3 to 5 using the 0.50 M and 0.25M acetic acid solution. Pipet 10mL of the aqueous solution for titration. 7. Calculate the concentration of the acetic acid in each solution. 8. Determine the values of K and n for the concentration used by the equation: K= Where; = concentration of the solute in the aqueous solution = concentration of the solute in the organic solvent n = ration of the average molecular weight of the solute in the solvent 1 to that in solvent 2 If the solute dissociates in aqueous solution, its average molecular weight in water decreases and n is greater than 1. If the solute associates in water solution, its average molecular weight in water increases and n is less than 1. 9. Record the results in the table. Experiment No. 4 DISTRIBUTION PRELAB EXERCISES: NAME: __________________________________________ PROFFESOR: ______________________________________ DATE: _________________ SCORE: ________________

1. Discuss Nernst Distribution Law, its application and limitations.

Experiment No. 4 DISTRIBUTION PRELIMINARY DATA SHEET

Date: _______________ Group No.: ___________ SIGNATURE Leader: ____________________________________ __________________________ Score: _______

Members:

____________________________________ ____________________________________ ____________________________________

____________________________ __________________________ __________________________

THEORETICAL FRAMEWORK: (PREPARE A FLOWCHART OF THE PROCEDURE OF THE EXPERIMENT) EXPERIMENTAL RESULTS AND OBSERVATION: A. Initial Concentration of Acetic Acid: 1.0M Solvent Trial 1 ___________ Water 2 ___________ Average 1 ___________ Ether 2 ___________ Average Xxx ___________ xxx __________ _ xxx __________ _ __________ _ ___________ __________ _ __________ _ xxx ___________ xxx __________ _ xxx __________ _ __________ _ ___________ __________ _ __________ _ V NaOH MNaOH Vsolution Msolution

B. Initial Concentration of Acetic Acid: 0.5 M Solvent Trial 1 ___________ ___________ __________ __________ V NaOH MNaOH Vsolution Msolution

_ Water 2 ___________ Average 1 ___________ Ether 2 ___________ Average xxx ___________ xxx __________ _ xxx ___________ __________ _ xxx ___________ xxx __________ _ xxx

_ __________ _ __________ _ __________ _ __________ _ __________ _

C. Initial Concentration of Acetic Acid: 0.25 M Solvent Trial 1 ___________ Water 2 ___________ Average 1 ___________ Ether 2 ___________ Average Xxx ___________ xxx __________ _ xxx __________ _ __________ _ ___________ __________ _ __________ _ Xxx ___________ xxx __________ _ xxx __________ _ __________ _ ___________ __________ _ __________ _ V NaOH MNaOH Vsolution Msolution

COMPUTATIONS FOR A, B AND C:

Concentration Range 0.50 1.0 M 0.25 0.50 M

K _____________ _____________

n _____________ _____________

GUIDED QUESTIONS AND PROBLEMS: 1. Does aetic acid dissociate or associate in water? Why?

2. How does dilution affect dissociation/association of acetic acid in water? Explain your answer.

Experiment 5 PHASE DIAGRAM OF A THREE-COMPONENT LIQUID SYSTEM OBJECTIVE: To prepare the phase diagram of a three-component liquid system. DISCUSSION: The composition of a ternary system may be described by one point in a triple coordinate diagram. The phase diagram of a ternary liquid system separating into two phases is given in Figure 1. The points on the dome (curve abcdefg), represent the compositions at which the two phases separate.
C
0.00 1.0

0.25

0.8

0.6 0.50

d c
0.75

0.4

e f
0.2

1.00

a
0.2 0.4 0.6 0.8

g
1.0

0.0

0.0

Figure 1. Phase diagram of a ternary system with two immiscible liquids, A and B.

Above this dome only a single phase, hence complete miscibility exists. At a composition described by a point under this dome, the system will separate into two phases. The a and g positions in Figure 1 indicate that there is slight miscibility between components A and B. If no miscibility existed between components A and B, the a position would coincide with corner A and the g position with corner B. The diagram also indicates that it is the third component, C, that is really miscible with either A or B in all proportions. In such a phase diagram the tie lines have a very important aspect: they connect the concentration of the two phases experimentally found to be in equilibrium with each other. For instance, when a mixture with composition h (Fig. 1) is prepared, it separates into two phases. Phase one (rich in A and C, and poor in B) has the composition designated on the diagram by b. Phase two (rich in B and C, but poor in A) has a composition designated by point f. The quantitative ratio of the two phases is given by, Phase _ one fh Phase _ two bh and, therefore, once a phase diagram is available it can be used to determine the compositions and proportions of the phases that would result when a mixture of specified overall composition is prepared. You may notice that the dome in Figure 1 is not symmetrical and the tie lines are not parallel to each other. This is simply because the solubility of C in the two phases (A and B) is not the same. In whatever direction the tie lines are slanted, they connect points of equilibrium compositions. These equilibrium compositions, b vs. f and c vs. e, become increasingly similar with each subsequent tie line, starting from the base of the dome and proceeding upward. Similarly, the tie lines become shorter and finally converge to a composition. This is called isothermal critical point or the plait point.

MATERIALS: CHCl, Glacial acetic acid, NAOH pellets, acid burets, 125-ml Erlenmeyer flasks, pipets PROCEDURE: A. Preparation of Solubility Curve:
1. Prepare 10-ml mixtures of H2O and CHCl containing the following % by volume of

water in 125-ml Erlenmeyer flasks: 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% and 90%. Measure the volume of each liquid accurately by using burets. 2. Titrate each solution from step 1 above with glacial acetic acid until the solution no longer turns cloudy when shaken vigorously. 3. Record the volume of each liquid in the table. 4. Calculate the weight of each liquid in each solution. 5. Calculate the % by weight of each liquid in each solution. 6. Plot the composition of the mixture on a Stokes and Roozeboom diagram (equilateral triangle) and connect the points to construct a solubility curve. Extrapolate the curve to zero on both ends. B. Construction of Tie-Lines 1. Prepare 20-ml mixtures of the three liquids with the following composition (% by volume): Mixture 1: 15% HOAc 25% CHCl 60% HO Mixture 2: 30% HOAc 25% CHCl 45% HO Mixture 1: 45% HOAc 25% CHCl 30% HO Mixture 1: 60% HOAc 25% CHCl 15% HO If no layers are formed, increase the amount of water until a considerable amount of the second layer can be observed.

2. Transfer each mixture into a separatory funnel, shake well for 2 minutes and allow the layers to separate. 3. Pipette 5.0 mL of each aqueous layer into previously weighted 250-mL Erlenmeyer flasks, then weigh again, Add 50 mL of distilled water and titrate to the phenolphthalein end point with 0.5 M NaOH. 4. Pipette 5.0 mL of each CHCl3 layer into previously weighted 250-mL Erlenmeyer flasks and weigh again. Add 50 mL water and titrate to the phenolphthalein end point with 0.25 M NaOH. 5. Calculate the percent by weight of acetic acid in each layer. 6. Locate the point on the solubility curve and construct the tie lines by connecting the compositions of the complementary layers with a straight line. 7. Determine the plaint point of the system.

Experiment No. 5 PHASE DIAGRAM OF A THREE-COMPONENTLIQUID SYSTEM PRELAB EXERCISES: NAME: __________________________________________ PROFFESOR: ______________________________________ 1). Define the following terms: a). Plait Point b). Solubility Curve c). Ternary Phase Diagram (Stokes and Roozeboom) d). Tie Lines DATE: _________________ SCORE: ________________

Experiment 5 PHASE DIAGRAM OF A THREE-COMPONENTLIQUID SYSTEM PRELIMINARY DATA SHEET

Date: _______________ Group No.: __________ SIGNATURE Leader: Members: ____________________________________ ____________________________________ ____________________________________ ____________________________________ __________________________ __________________________ __________________________ __________________________ Score: _______

THEORETICAL FRAMEWORK: (PREPARE A FLOWCHART OF THE PROCEDURE OF THE EXPERIMENT) EXPERIMENTAL RESULTS AND OBSERVATION: Mixture No. 1 2 3 4 5 6 7 8 9 Volume of liquid HO HOAc CHCl Weight of liquid HO HOAc CHCl % by Weight HO HOAc CHCl

_____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____

_____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ dD _____ _____ _____ _____ _____ _____

_____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____ _____

Density of HO:__________Density of HOAc:____________Density of CHCl:___________ B. Tie Lines: Mixture No. Aqueous Layer Weight V of NaOH % HOAc CHCl3 Layer Weight V of NaOH % HOAc 1 __________ __________ __________ __________ __________ __________ 2 __________ __________ __________ __________ __________ __________ 3 __________ __________ __________ __________ __________ __________ 4 __________ __________ __________ __________ __________ __________

Draw a Ternary Phase Diagram of Water-Acetic Acid-Chloroform System: (Separate Sheet of Paper)

Experiment 6 ADSORPTION OBJECTIVES: 1) To determine the saturation value for monomolecular coverage for the adsoprtion of acetic acid by activated charcoal 2) To determine the values of the constant k and n in the Freundlich equation. 3) To determine the values of the constant a and b in Langmuirs equation. DISCUSSION: Adsorption is a surface phenomenon. It consists of an interaction between the moving molecules of a liquid or gas phase and the relatively fixed molecules comprising a surface or interface. (In this discussion the term molecule will be used generically to include atoms and ions as well as molecules). The moving molecules become bound to the surface more or less strongly. Adsorption processes may be classified as physical or chemical. Another classification is reversible and irreversible, referring to the comparative ease of removal, desorption of the bound molecules. Generally, physical adsorption (physisorption) is reversible, while the chemical type (chemisorptions) is irreversible. The adsorbed molecules may come from a gas phase, a liquid or from a solution in a liquid. The adsorbing surface may be either liquid or solid. Adsorption from solution is usually monomolecular (monolayer coverage); i.e. adsorption ceases when the surface is completely covered with a layer of one molecular thick. Adsorbed layers more than one molecular thick have been proved to exist in certain cases as yet rare. The amount of adsorption varies with the concentration of the solution. There are two equations for this relationship for monomolecular adsorption. One is the empirical Freundlich equation: = KCn or log ( ) = log k + n log C

in which x/m is the weight of the absorbed material per gram of adsorbent and C is the concentration of the solution at equilibrium. The term k and n are constants to be evaluated from experimental data in each case.

in which x/m and C have the same significance as above, a is a constant proportional to the heat of adsorption and the temperature, and b is the amount of adsorption when the surface is covered with a monomolecular film. Langmuirs equation is based on the assumption that the solid surface is completely uniform. Deviations from the equation indicate lack of uniformity in the surface.

PROCEDURE: 1) Prepare 100 mL each of the following solutions by serial starting from glacial acetic acid(17 M): 1.0 M, 0.50 M, and 0.0625 M. 2) Measure 50 mL of the 1.0 M solution into a 125 mL Erlenmeyer flask, add 1.0 gram of accurately weighed activated charcoal, shake the mixture and allow to equilibriate for one hour. Agitate the mixture from time during the equilibriation process. 3) While equililbriation is taking place, pipet 5.0 mL of the original solution into a 250 mL Erlenmeyer flask and titrate with standard 1.0 M NaOH to the phenolpthalein end point. Calculate the original concentration of the solution from the titration data. 4) After equilibriation, filter off the activated carbon and titrate 5.0 mL of the filtrate with 0.1 M NaOH to the phenolphthalein end point. 5) Repeat steps 2 to 4 using the other solutions prepared in step 1. For the titration, use 10.0 mL for the last three soultions. 6) Calculate the equilibrium concentration (C2) and the specific adsorption (y) for each concentration.

7) Plot y versus C1 and determine the saturation value for monomolecular coverage. 8) Plot log y versus log C1 to determine the saturation value for monomolecular coverage. 9) Plot (C1/y) versus C1 to determine a and b in Langmuirs Equation.

Experiment No. 6 ADSORPTION PRELAB EXERCISES: NAME: __________________________________________ PROFFESOR: ______________________________________ DATE: _________________

1). Distinguish between the following adsorption isotherms: Langmuir, BET, Temkin and Fruendlich.

2). The data given below for the adsorption of CO on charcoal at 273 K. Confirm that they fit the Langmiur isotherm, and find the constant K and the volume corresponding to complete coverage. In each case V has been corrected to 1.00 atm (101.325 kPa). P(kPa) V(cm3) 13.3 10.3 26.7 19.3 40.0 27.3 53.3 34.1 66.7 40.0 80.0 458.5 93.3 48.0

Experiment 6 ADSORPTION PRELIMINARY DATA SHEET

Date: _______________ Group No.: ___________ SIGNATURE Leader: Members: ____________________________________ ____________________________________ ____________________________________ ____________________________________ __________________________ __________________________ __________________________ __________________________ Score: _______

THEORETICAL FRAMEWORK: (PREPARE A FLOWCHART OF THE PROCEDURE OF THE EXPERIMENT) EXPERIMENTAL RESULTS AND OBSERVATION:

Initial Conc (C1) ____________ ____________ ____________ ____________ ____________

Final Conc (C2) ____________ ____________ ____________ ____________ ____________

Wacetic acid ____________ ____________ ____________ ____________ ____________

mcharcoal ____________ ____________ ____________ ____________ ____________

y ____________ ____________ ____________ ____________ ____________

SAMPLE COMPUTATION:

Plot y versus C1

Saturation value for y monomolecular coverage = _____________________________

Plot of log y versus C1

Freundlichs constant: n =___________________________ k=____________________________

Plot of log (C1/y) vs C1

Langmuirs constants: a = ______________________________ b =______________________________

Experiment 7 CHEMICAL EQUILIBRIUM OBJECTIVE: To be able to determine the equilibrium constant for the system: Fe3+ + CNS Yellow DISCUSSION: The word equilibrium suggests balance or stability. The fact that a chemical reaction occurs means that the system is not in equilibrium. The process will continue until the system reaches equilibrium. At this point, there is no observable change in the concentrations of reactants and products. While the reaction appears to stop, the reality is that reactants are being converted to products at the same rate that products are being converted to reactants. These principles can be illustrated with a generic reaction: aA + bB cC + dD If only A and B are present, the reaction will proceed to the right; if only C and D are present, the reaction will proceed to the left. In both cases, the reaction will apparently stop when equilibrium is reached.This state is characterized by a specific value for the equilibrium constant K, defined for this reaction by the following expression. colorless F eCNS2+ blood-red

K= Here the brackets signify the equilibrium concentrations (in M) of the various species. Note that the coefficients in the balanced equation appear as exponents in the equilibrium constant and that the products always appear in the numerator and the reactants in the denominator. The value of the equilibrium constant depends on the chemical reaction and on temperature. However, the value of K will not depend on the initial concentrations of reactants and products. Furthermore, the specific mathematical form of the equilibrium constant must correspond to the correct chemical equation for the reaction. If the equation is not correct for example, if the

formula of one or more of the species is wrong the value of K, even if calculated using accurate concentrations and making no numerical errors, will not be constant. 3+ In this experiment you will investigate the reaction of the Fe [iron(III), or ferric] ion with the SCN (thiocyanate) ion. The product of this reaction is a complex ion that imparts a red color to aqueous solution. You are asked to experimentally determine the formula for the complex ion and a numerical value for the equilibrium constant for the reaction in which it is formed. PROCEDURE: 1. Label 5 clean and dry test tube of identical size and make. 2. Prepare solutions of Fe(NO3)3 by serial dilution as follows: a.) Place 20 mL of 0.20 M Fe(NO3)3 in a 25-mL graduated cylinder. b.) Transfer 8 mL of the solution into test tube 1. c.) Add distilled water to the remaining solution in the graduated cylinder to bring the volume to 20 mL. d.) Transfer 8 mL of diluted solution into test tube 2. e.) Repeat procedures c and d until 5 different concentrations of Fe(NO3)3 are obtained.

3. Add 8 mL of 0.002 M KCNS to each diluted solutions from step 2.

4. Wrap each test tube with white paper.

5. By looking down into the solutions in the test tube, compare the color intensities of the solutions in test tubes 1 and 2. (The process may be aided by placing a mirror below the test tubes).

6. Adjust the height of the solution in test tube 1 by removing or adding some solution until the observed color intensities appear to be equal. Transfer the solution in test tube 1 to clean container with the aid of dropper.

7. Measure the heights of the solutions in test tubes 1 and 2 by means of a ruler.

8. Repeat steps 5, 6 and 7 with the test tubes 3, 4 and 5.

9. Record all measured heights of solution.

10. By assuming that all the limiting reagent in test tubes 1 was converted to the complex, calculate the concentration of the complex in test tubes 2 to 6 by using test tube 1 as standard and by applying Beer-Lamberts law:

CS x hs = CU x hu Where: CS=concentration of the standard hs= height of the standard CU=concentration of the unknown hU=height of unknown

11. Calculate the equilibrium concentrations of the reactant. [Reactants] equilibrium = [Reactants]initial [Reactants]converted

12. Record all the data in the table. Experiment No. 7 CHEMICAL EQUILIBRIUM PRELAB EXERCISES: NAME: __________________________________________ PROFFESOR: ______________________________________ DATE: _________________

1. Discuss Beer-Lamberts Law, its application and limitations.

Experiment 7 CHEMICAL EQUILIBRIUM PRELIMINARY DATA SHEET

Date: _______________ Group No.: ___________ SIGNATURE Leader: ____________________________________ __________________________ Score: _______

Members:

____________________________________ ____________________________________ ____________________________________

__________________________ __________________________ __________________________

THEORETICAL FRAMEWORK: (PREPARE A FLOWCHART OF THE PROCEDURE OF THE EXPERIMENT) EXPERIMENTAL RESULTS AND OBSERVATION: Test Tube No. Before [Fe3+] Mixing After Mixing [CNS ] ________ [Fe ] ________ [CNS-] ________ hs (height of standard) xxx hu (height of unknown) xxx [Fe3+] xxx [CNS-] xxx [FeCNS2+] ________ keq xxx Computation of Average Keq: ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________ ________
3+ -

1 ________

2 ________ ________

3 ________ ________

4 ________ ________

5 ________ ________

GUIDE QUESTIONS AND PROBLEMS: 1. How is the value of the equilibrium constant affected by the concentration of the reactants used?

2. How do you explain the above observation?

3. What factors affect the value of the equilibrium constant?

Experiment 8 CHEMICAL KINETICS OBJECTIVES: 1. To determine the order of the reaction 2. To determine the activation energy of both uncatalyzed and catalyzed reactions. DISCUSSION: Chemical reactions occur at varying speeds with a vast spectrum of rates, ranging from very slow to extremely fast. For example, the rusting of iron is fairly slow, whereas the decomposition

of TNT proceeds explosively fast. Experiments have shown that the rate of a homogeneous reaction in solution depends upon the nature of the reactants, their concentrations, the temperature of the system, and the use of catalysts. Consider the hypothetical reaction: A+B C+D

The rate of this reaction may be measured by observing the rate of disappearance of the reactants A or B, or the rate of appearance of the products C or D. Which species is observed is a matter of convenience. For example if A, B, and C are colorless and D is colored, the rate of appearance of D can be conveniently measured by observing an increase in the intensity of the color of the solution as a function of time. Mathematically, the rate of reaction may be expressed as follows

Rate of disappearance of A =

=-

Rate of appearance of D =

In general, the rate of the reaction depends upon the concentration of one or more of the reactants. Thus, the rate of the hypothetical reaction above may be expressed as: Rate = k[A]x [B]y where [A] and [B] are the molar concentrations of A and B, x and y are the powers to which the respective concentrations must be raised to describe the rate, and k is the specific rate constant. The values of x and y must be determined experimentally. For example, if x = 2 and y = 1, then the rate law is: Rate = k[A]2 [B] The rate of reaction depends on concentration, temperatures, catalysts and inhibitors. MATERIALS: Zn metal, concentrated HCl, 1M Cu(NO3)2 solution, 30-mL test tubes, stopper fitted with rightangle delivery tube, water bath. PROCEDURE: A. Effect of Concentration

1. Prepare by serial dilution from concentrated HCl, 5M, 4M, 3M, 2M and 1M solutions. 2. Place 10-mL of 1M HCl in a clean and dry 30-mL ignition tube, add a piece of Zn metal and close with a stopper fitted with a right-angle and delivery tube. 3. Dip the tip of the delivery tube in a beaker of water and measure the time required for 30 bubbles to emerge from the tip of the delivery tube. 4. Change the ignition tube with a clean and dry one, place 10-mL of 2M HCl and add Zn. (You may use the unreacted Zn from the previous step after rinsing it well.). Repeat steps 2 and 3. 5. Do steps 2 and 3 using 3M, 4M and 5M HCl. 6. Formulate the rate law. Determine the values of k and n in the rate law. B. Effect of Temperature 1. Place 10-mL of 2M HCl in a clean, dry ignition tube and warm in a water bath until the temperature of the HCl solution reaches 40C. Remove the tube from the water bath, add a piece of Zn and fit the tube with the delivery tube. 2. Determine the time required for 30 bubbles to emerge from the tip of the delivery tube. 3. Repeat steps1 and 22 using temperatures of 50C, 60C and 70C. 4. Determine the values of k from the rate using data obtained from procedure A. 5. Plot log k versus 1/T and determine the activation energy of the reaction by using the Arrhenius equation:

C. Effect of Catalyst 1. Place 10-mL of 2M HCl and 2-mL of 1M Cu(NO3)2 in a clean and dry ignition tube. Heat the solution in the tube to 40C in a water bath. Remove the test tube from the water bath, add a piece of Zn and fit with the delivery tube. 2. Determine the time required for 30 bubbles to emerge from the tip of the delivery tube. 3. Repeat steps 1 and 2 at 50C, 60C and 70C. 4. Determine the values of k from the rate using data obtained from procedure A. 5. Plot log k versus 1/T and determine Ea for the catalyzed reaction. Experiment No. 8 CHEMICAL KINETICS PRELAB EXERCISES: NAME: __________________________________________ DATE: _________________

PROFFESOR: ______________________________________ 1. The rate constant for the first order decomposition of a compound A in the reaction 2A P is k=2.78 x10-7 s-1 at 25C. What is the half life of A? What will be the pressure, initially 32.1 kPa, (a) 10 s, (b) 10 minutes after initiation of the reaction?

2. The rate constants for the decomposition of certain substance is 1.70 x 10 -2 L mol-1s-1 at 24C and 2.01 x 10-2 L mol-1s-1 at 37C. Evaluate the Arrhenius parameters of the reaction.

Experiment 8 CHEMICAL KINETICS PRELIMINARY DATA SHEET

Date: _______________ Group No.: ___________ SIGNATURE Leader: Members: ____________________________________ ____________________________________ ____________________________________ ____________________________________ __________________________ __________________________ __________________________ __________________________ Score: _______

THEORETICAL FRAMEWORK: (PREPARE A FLOWCHART OF THE PROCEDURE OF THE EXPERIMENT) EXPERIMENTAL RESULTS AND OBSERVATION: A. Effect of Concentration Concentration 1M 2M 3M 4M 5M time ______________ ______________ ______________ ______________ ______________ Rate (1/time) ____________ ____________ ____________ ____________ ____________

Plot of Rate vs. [HCl]

Rate law: k= B. Effect of Temperature t (C) 40 50 60 70 T(K) _____ _____ _____ _____ _____ _____ _____ _____ time _____ _____ _____ _____ _____ _____ _____ _____ k _____ _____ _____ _____ n=

Plot of log k vs. 1/T

Rate law: slope = C. Effect of Catalyst t (C) 40 50 60 70 T(K) _____ _____ _____ _____ _____ _____ _____ _____ time _____ _____ _____ _____ _____ _____ _____ _____ k _____ _____ _____ _____ Ea=

Plot of log k vs. 1/T

Rate law: slope = GUIDED QUESTIONS AND PROBLEMS: 1. Why is the reaction rate independent of the amount of Zn used in the experiment? Ea=

2. How does trebling the concentration of HCl affect the reaction rate?

3. How does the activation energy of the catalyzed reaction compare with that of the uncatalyzed reaction?

Experiment 9 GALVANIC CELLS

OBJECTIVES: 1. To be able to assemble galvanic cells. 2. To be able to measure the potentials to test electrodes. 3. To be able to measure the potential of a galvanic cells.

DISCUSSION*: Oxidation and reduction reaction occur simultaneously side by side. A reduction reaction occurs only if an oxidation reaction occurs and vise versa. Electrons are given in oxidation while in reduction electrons are gained. Oxidizing agent is a chemical substance which has a large tendency to gain electrons, while reducing agent is a chemical substance causes other substances to be reduced and itself oxidized. Example for an oxidation-reduction reaction: 2Ag+(aq) + Cu(s) 2Ag(s) + Cu2+(aq)

We can see that Cu(s) converts to Cu2+ (Oxidation). While Ag+(aq) changes to Ag(s) (reduction). The oxidation-reduction reaction can be divided into two half reactions, one for oxidation and the other is reduction reaction: Cu(s) 2Ag+(aq) + 2eCu2+(aq) + 2e2Ag(s) (Oxidation) (Reduction)

The reduction equation is multiplied by 2 because the number of electrons given in the oxidation reaction must be equal to the number of electrons gained in the reduction reaction.

Notice, that pure silver is formed out of the solution of silver salt. Therefore, this process can be used to produce solid metals out of salts of the same metal. The above reaction is a general process of replacement. When an element, which is more reactive electrochemically, reacts with aqueous solution of salt of metal, which is more reactive electrochemically, displacement reaction will occur. Another Example: Zinc reacts with copper sulphate, because zinc is more reactive electrochemically than copper. Therefore, when a strip on zinc in placed in a copper sulphate solution, the strip is "solvated" in to solution according to the equation: CuSO4(aq) + Zn(s) Cu(s) + ZnSO4(aq) Also we can write this reaction into two half reactions Cu2+(aq) + 2e- Cu (s) Zn(s) Zn2+(aq) + 2e(reduction). (oxidation).

Other application of redox reactions is constructing electrochemical cells, which have two types: Galvanic cells: electrochemical cells in which redox reaction occurs spontaneously and in which chemical energy converts to electrical energy. Electrolytic cells: electrochemical cells which uses energy from other source to induce redox reactions and in which electrical energy converts into chemical energy.

Electrochemical cell composed of two electrodes each of them immersed in a certain electrolytic solution. Electricity can pass through the cell if 1. 2. Electrodes connected by a conductor (metal wire) Both electrolytic solutions must be connected by a way through which certain ions are allowed to pass from one solution to another.

The following figure shows a Galvanic cell in which a total redox reaction occurs.

In this system, an oxidation reaction occurs in beaker 1 where atoms of Zn moving out of the zinc electrode, leaving behind two electrons who travels along the metal wire towards the copper electrode. Therefore the anode becomes smaller as the redox reaction proceeds. In beaker 2, a reduction reaction occurs where ions of copper are attracted to the cathode, receive two electrons and precipitate on the electrode as copper atoms. Therefore the cathode becomes bigger as the redox reaction proceeds. The salt bridge enables SO42-(aq) to travel between the beakers and close the electric circuit and retain equilibrium of electric charges in the system. The redox reaction continues until the system reaches chemical equilibrium.

An electrochemical cell is written in the following way: Zn(s) | Zn2+(aq) || Cu2+ (aq) | Cu(s)
Anode is always written on the left side Cathode is always written on the right side

Represents the salt bridge

* http://www.sep.alquds.edu/ MATERIALS: Cu wire, Zn metal, Pb wire, graphite rod, Zn2+ solution, Pb2+ solution, SO42- solution, Fe2+ solution, Fe3+ solution, Cu2+ solution, KCl or KNO3, KmnO4, concentrated H2SO4.

PROCEDURE: A. Preparation of Cu/Cu2+ Reference electrode

1. Secure a 4-to 5-cm long glass pipet or dropper. Plug the tapered end of the pipet with a small ball of cotton pushed down the pipet with a stif wire. Make sure that the cotton is tightly packed and that it reaches up to the opening of the pipet. 2. Immerse the tip of the pipet in a beaker containing a saturated solution of KCL or KNO3 until the cotton is fully soaked. 3. Fill the pipet with 0.1 M CuSO4 solution using another pipet with a rubber bulb. 4. Get a metal rod with a ciameter smaller than the inner diameter of the pipet. Coil a copper wire around the rod leaving some portion uncoiled for the voltmeter leads. 5. Insert the coiled wire into the pipet. Plug the open portion of the pipet with modeling clay to fix theposition of the wire. This will also seal the tube and prevent the leakage of the copper sulfate solution.

Alternative Procedure A.

1. Secure a 4-to 5- inch long copper wire and dip into a beaker containing 0.1 M CuSO4 solution. Prepare a salt bridge as follows: Cut a piece of filter paper into a 1- cm wide, 8-to 10- cm long strip and dip into a saturated solution of KCl or KNO3. Use a fresh strip for a new solution. DO NOT USE THE STRIP WITH TWO DIFFERENT SOLUTIONS.

B. Determination of Electrode Potentials 1. Assemble the following test half-cells: a. Zn/Zn2+ electrode: Dip a piece of Zn metal strip (approximately 5 cm long, 1 cm wide) in a 50mL beaker containing 25 mL of 0.1 M ZnSO4. b. Pb/Pb2+ electrode: Dip a 10-cm long Pb wire in a 50-mL beaker containing 0.1 M Pb(NO3)2. c. C/Fe2+, Fe3+ electrode: Dip a graphite rod in a 50-mL beaker which contains 12.5 mL of 0.2 M Fe(NH4)2(SO4)2 and 12.5 mL of 0.2 M FeNH4(SO4)2. d. Pb/PbSO4(S), SO42- electrode: Dip a lead wire coated with PbSO 4 in a 50 mL beaker which contains 25 mL of 0.1 M k2SO4. ( To prepare the wire, dip a Pb wire in a solution of 6 M H 2SO4 until the wire becomes coated with PbSO4, a white powdery substance). 2. Set up a cell by coupling a Cu/Cu 2+ electrode with one of the assembled half-cells. If the reference electrode is that prepared by the first procedure, simply dip the electrode into the electrolyte of the test electrode. If the second type of Cu/Cu2+ electrode is used, connect the two solutions by dipping one end of the filter paper stip in the CuSO 4 solution and the other end in the electrolyt of the test electrode. 3. Measure the voltage of the cell by connecting the Cu/ Cu 2+ reference electrode to the positive (red) terminal of a digital voltmeter and the metal strip or wire or carbon rod of the test electode to the negative (black) terminal. 4. For the Cu/Cu2+ reference electrode (cathode), the reduction half-reaction and the corresponding potential is: Cu2+ + 2 eCu(S) = 0.34 volt

The measure potential of the cell is the difference in reduction potentials of the cathode (reference electrode) and the anode (test electrode). 5. Record your data on the table provided in the data sheet.

C. Electromotive Force of Galvanic Cells

1. Assemble the following cells by coupling two test electrodes. Connect the two test electrodes by dipping the ends of a salt bridge (filter paper stip soakeed with saturated KCl or KNO3) into solutions. Cell A: Zn/Zn2+ and Pb/Pb2+ electrodes Cell B: Zn/Zn2+ and C/Fe2+, Fe 3+ electrodes Cell C: Pb/Pb2+ and C/Fe2+, Fe3+ electrodes Cell D: Zn/Zn2+ and Pb/PbSO4(S), SO42-electrodes 2. Connect each electrode to the input terminals of the voltmeter and read the voltage. If a negative voltage is observed, interchange the terminal connections. Note the polarity of the electrodes. The cathode is the half-cell connected to the positive (red) terminal of the meter, and the anode is the half-cell connected to the negative (black) terminal. 3. Record the observed cell potentials: 4. Write the cell reactions and determine the theoretical electromotive force of each galvanic cell using values of electrode potentials from tables.

D. Variation of Electrode Potential with Electrolyte Concentration 1. Prepare several solutions containing varying concentrations of MnO4- and Mn2+ ions. By using a pipet, measure the following volumes of 0.02 M KmnO4 and 0.05 M Na2C2O4 solution into a 100-mL beaker and mix the resulting solution well. Mixture 1 2 3 4 mL of KmnO4 30 35 20 25 mL of Na2C2O4 5 10 15 20

2. Measure the reduction potential of each mixture using a Cu/Cu2+ reference electrode. 3. Determine the concentration of MnO4- and Mn2+ ions in each mixture. 4. Record the data in the table. 5. Plot cell versus log ([MnO4-]/Mn2+]). Determine the slope of the best straight line.

6. Based on the slope obtained in step 5, derive an expression relating the cell potential and the concentrations of MnO4- and Mn2+ ions in the electrode.

Experiment No. 9 GALVANIC CELLS PRELAB EXERCISES: NAME: __________________________________________ PROFFESOR: ______________________________________ 1. Distinguish between galvanic and electrolytic cells. DATE: _________________

2. Distinguish between cell potential and electromotive force.

3. Describe a method for the determination of standard potential of a cell.

Experiment 9 GALVANIC CELLS PRELIMINARY DATA SHEET

Date: _______________ Group No.: ___________ SIGNATURE Leader: Members: ____________________________________ ____________________________________ ____________________________________ ____________________________________ __________________________ __________________________ __________________________ __________________________ Score: _______

THEORETICAL FRAMEWORK: (PREPARE A FLOWCHART OF THE PROCEDURE OF THE EXPERIMENT) EXPERIMENTAL RESULTS AND OBSERVATION:

A. Determination of Electrode Potentials

Test Electrode

Reduction Half- Reaction

Ecell

Eanode

Zn/Zn2+

_____________________________

________

________

Pb/Pb2+

_____________________________

________

________

C/Fe2+, Fe3+

_____________________________

________

________

Pb/PbSO4(s), SO42-

_____________________________

________

________

II. Electromotive Force of Galvanic Cells Cell A. Zn/Zn2+ and Pb/Pb2+ B. Zn/zn2+ and C/Fe2+, Fe3+ C. Pb/Pb2+ and C/Fe2+, Fe3+ D. Zn/Zn2+ and Pb/PbSO4(s), SO4 Anode
____________

Cathode
_____________

Ecell( observed)
_______________________

____________

_____________

_______________________

____________

_____________

_______________________

____________

_____________

_______________________

Cell A: Anode :

Reaction _______________________________________________

0 ___________ ___________ ___________

Cathode : _______________________________________________ Cell : _______________________________________________

Cell B: Anode :

Reaction _______________________________________________

0 ___________ ___________ ___________

Cathode : _______________________________________________ Cell : _______________________________________________

Cell C: Anode :

Reaction _______________________________________________

0 ___________ ___________ ___________

Cathode : _______________________________________________ Cell : _______________________________________________

Cell D: Anode :

Reaction _______________________________________________

0 ___________

Cathode : _______________________________________________ Cell : _______________________________________________

___________ ___________

III. Variation of Electrode Potential with Concentration

Mixture 1

[MnO4]] ________

[Mn2+] _________

log ([MnO4-]/[Mn2+]) _________________________

Ecell

____________ 2 ________ ____________ 3 ________ ____________ 4 ________ ____________ _________ _________________________ _________ _________________________ _________ _________________________

Plot of log ([MnO4]/[Mn2+]) vs. cell

Slope =__________________

y-intercept =________________

Equation for cell:

GUIDE QUESTIONS AND PROBLEMS:

1. Does the curve obtained obey the Nernst equation? Why?

2. What is the significance of the slope of the line? How does it compare with the theoretical value?

3. What is the significance of the value of the y-intercept obtained in your plot? How does it compafre with the theoretical value?

Experiment 10

CONDUCTIMETRY

OBJECTIVES: 1. To be able to determine the relative mobilities of some ions in solution. 2. To be able to determine the variation of conductance with concentration of electrolytes. 3. To be able to determine the concentration of an electrolyte by conductance measurement.

DISCUSSION: As its name implies, conductimetry is concerned with the electrical conductivity of electrolytes. Measurements are made indirectly across the resistance of the solution with alternating current, since direct current would alter the composition of the sample solution by electrolysis. Experience has shown that for reasons related to the measuring technique (polarization phenomena) better results are obtained when the measuring frequency is adapted to the range of measurement. The conductivity of a solution depends on: The quantity of ions. The more ions a solution contains, the higher will be its conductivity. The kind of ions. The smaller and more mobile an ion, the better will be its electrical conductivity. Thus H3O+, OH-, K+ and Cl- ions all conduct very well. The solvent. The more polar the solvent, the better the ionisation of the solutes it contains. In relation to this, water is an ideal solvent, while methyl alcohol is also good. The temperature. Ionic mobility increases with rising temperature. According to the type of ion, the conductivity increases by 1-3% / C. In conductimetric titrations, the cell constant does not usually need to be known, since only the change in conductance during the titration is tracked. MATERIALS: Conductance apparatus (two graphite rods connected in series with a 9-V cell and a digital multimeter), buret, 0.1M HCl, 0.1 M NaOH, 0.1 M NaCl, 0.1M NH4C2H3O2.

PROCEDURE:

A. Determination of Relative Ionic Mobility 1. Place 20 mL of the following solutions in 50-mL beakers: a. 0.1 M HCl solution b. 0.1 M NaOH solution c. 0.1 M NaCl solution d. 0.1 M NH4Cl solution e. 0.1 M NaC2H3O2 solution

2. Measure the conductance of each solution by dipping the probes in the solution and reading from the multimeter the current flowing through the solution. (NOTE: Wash the probe with distilled water and dry with tissue paper before immersing it into the solution. 3. Tabulate in incrasing order of magnitude the current observed for the solutions containing the chloride ion. Determine from the results the relative mobility of the cations in the solutions. 4. Tabulate in increasing order of magnitude the current observed for the solutions containing the sodium ion. Determine from the results the relative mobility of the anions in the solutions.

B. Variation of conductance with Concentration

1. Prepare different concentrations of hydro chloric acid by measuring with a pipet the following volumes of liquid into 50-mL beakers:

Mixture 1 2 3 4 5

mL of 1 M HCl 5 10 15 10 25

mL of distilled water 20 15 10 15 0

2. Measure the conductance of each mixture. Calculate the concentration of HCl in the mixture and record the data in the table. 3. In the absence of extraneous effects, it is expected that the conductance of the electrolyte is directly proportional to the concentration of the electrolyte (that is, if the electrolyte concentration is doubled, the conductance of the solution should be doubled). Based on this premise and on the measured conductance of the most dilute solution, calculate the expected conductance of each mixture preapared in step 1. 4. Plot the concentration of HCl against the (a)measured conductance and (b) calculated conductance from step 3 on the same graphing paper. 5. Compare the curves obtained in step 4 and explain the difference between the observed and expected behavior.

C. Conductimetric Titration

1. Transfer 25.0 mL of the analyte into a 100-mL beaker, dip the probe in the solution and take the multimeter reading. 2. Slowly add 1 mL increments of the titrant from a buret mixing the reaction mixture well and recording the multimeter reading after each addition. Stop adding the titrant when the multimeter reading no longer shows appreciable change in slope. ( This would be when appoximately 35 mL of titrant has been added.) 3. Tabulate the meter readings and the total volume of titrant added.

4. Plot the meter reading against the total volume of titrant added. 5. Determine from the titration curve the volume of the titrant needed to reach the equivalence point. 6. Calculate the concentration of the analyte.

Experiment No. 10 CONDUCTIMETRY PRELAB EXERCISES: NAME: __________________________________________ PROFFESOR: ______________________________________ 1. Discuss the following: a. Conductance and Conductivity b. Strong and Weak Electrolytes c. Mobilities of ions and Conductivity DATE: _________________

Experiment 10 CONDUCTIMETRY PRELIMINARY DATA SHEET

Date: _______________ Group No.: ___________ SIGNATURE Leader: Members: ____________________________________ ____________________________________ ____________________________________ ____________________________________ __________________________ __________________________ __________________________ __________________________ Score: _______

THEORETICAL FRAMEWORK: (PREPARE A FLOWCHART OF THE PROCEDURE OF THE EXPERIMENT) EXPERIMENTAL RESULTS AND OBSERVATION:

A1. Determination of Relative Ionic Mobility

Solution

I (mA)

Hydrochloric acid Sodium hydroxide Sodium chloride Ammonium chloride Sodium acetate

__________ __________ __________ __________ __________

A2. Relative Mobility of Cations

Cation

I(mA)

Conclusion

H+ _________________ ________________________

Na+ _________________ ________________________

NH4+ _________________ ________________________

A3. Relative Mobility of Anions

Anion

I(mA)

Conclusion

OH-

___________________________

____________________________________

Cl__________________ ________________________

C2H3O2__________________ ________________________

Relative Mobility:

B. Variation of Conductance with Concentration

Mixture mL of 1 M HCl mL of distilled H2O

[HCl]mixture Measured

I(mA) Expected

20 ____________

______________

_________

10

15 ____________

______________

_________

15

10 ____________

______________

_________

20

5 ____________

______________

_________

25

0 ____________

______________

_________

Plot of [HCl] vs. Conductance (mA)

Compare the curves (a) and (b) and explain the difference between observed and expected bahavior.

C. Conductimetric Titration

Vtitrant

I(mA)

Vtitrant

I(mA)

Vtitrant

I(mA)

______ ______ ______ ______ ______

______ ______ ______ ______ ______

______ ______ ______ ______ ______

______ ______ ______ ______ ______

______ ______ ______ ______ ______

______ ______ ______ ______ ______

Conductimetric titration Curve (Plot of Vtitrant vs. Conductance)

Vtitrant at equivalent point Concentration of Unknown

= _________________________ =__________________________