Experiment 3: The Copper Cycle Isuri Vidyarathne (6427761), November 01, 2013 Partner: Josh Taylor TA: Philip

Bulsink Experimental Objectives: The purpose of this lab is to explore the Copper Cycle and the different methods of extraction it entails such as by pyrometallurgical or hydrometallurgical processes. The end of the experiment should have the entire amount of initial copper showing that during efficient extraction, no copper should theoretically be lost. Procedure: Refer to Lab Manual Pg. 17-19 CHM2353 Descriptive Inorganic Chemistry Laboratory Observations: Steps: Step 1: Cu to Cu(NO3)2 Step 2: Observations: -Solution turned a rich transparent green, brown/reddish fumes were emitted as

Results: Table 1:

HCl [ ] Initial Ion [ ] Volume (mL)

Mg(OH)2 0.002 M Saturated 50

Ca(OH)2 0.002 M Saturated 1.0

Sr(OH)2 0.002 M Saturated 0.5

Vi HCl Vf HCl Delta HCl #1 Vi HCl Vf HCl Delta HCl #2 Vi HCl Vf HCl Delta HCl #3 Avg. mol HCl Avg. mol Ion Avg. [Ion] Avg. [OH-] Avg. ~Ksp Literature Ksp12

0.00 9.50 9.50 mL 9.50 18.10 9.40 mL 0.00 9.50 9.50 mL 1.9x10-5 9.5x10-6 1.9x10-4 3.8x10-4 2.7x10-11 1.8x10-11

17.80 10.10 7.70 mL 24.10 17.80 6.30 mL 31.75 24.10 7.65 mL 1.4x10-5 7.0x10-6 7.0x10-3 1.4x10-2 1.4x10-6 5.5x10-6

33.50 31.75 1.75 mL 34.60 33.50 1.10 mL 35.70 34.60 1.10 mL 2.6x10-6 1.3x10-6 2.6x10-3 5.3x10-3 7.3x10-8 6.4x10-3

On Table 1. after the three titrations for each Group II hydroxide have been recorded with initial and final volume values, the average number of HCl moles needed for the titration has been calculated. With that number, using the ratio 2:1 HCl to Ion mole ratio, the moles and concentration of the Ion has been calculated. The OH- concentration has also been calculated and with that all the average Ksp values are listed, including their respective literature values. The first three trials required 9.50mL, 9.40mL, and 9.50mL of HCl respectively to titrate 50mL of saturated Mg(OH)2. The average of the amount of HCl moles to titrate the base in all 3 samples is calculated at the bottom of Table 1. Included is the average concentration of Mg2+ and OH- required for the Ksp as well as the Ksp number compared to the literature Ksp number. Similarly, for Ca(OH)2s titration, the three volumes of HCl are 7.70mL, 6.30mL, and 7.65mL respectively. They are the volumes required for the titration of 1mL of Ca(OH)2. The table also has information on the average number of HCl and Ca 2+ moles needed for all three titrations samples. It also has the concentrations of the ion and hydroxide. The Ksp value is also listed and compared to the literature value. All the results for Sr(OH)2 are also calculated in the same order as the previous samples are and listed on Table 1. The three amounts of HCl obtained from the trials are 1.75mL, 1.10mL, and 1.10mL.

Sr(OH)2 : www.arschemia.net/Permanent_Files/Tables/Solubility_Product_Constant.pdf Mg(OH)2 and Ca(OH)2 : www.bilbo.chm.uri.edu/CHM112/tables/KspTable.htm

The sample calculations required for finding the moles of ions, concentration of ions, and Ksp values are listed below: First trial of Mg(OH)2 titration: ( )
( ) ( ) ( ) ()

n=9.5x10-6 V=50 mL C=1.9x10-4mol

C=0.002 M V=0.0095 L n=1.9x10-5mol

Finding the concentration of the Mg2+:

Finding Ksp of Mg(OH)2:

( )
( ) ( ) ( )

Ksp = [Mg2+][OH-]2
( ( )( ) )

Ksp = (1.9x10-4)(3.8x10-4)2 Ksp = 2.7x10-11

Discussion: The objective of this lab is to examine whether there is a periodic trend in the solubility of metal hydroxides in Group II. We used titration with HCl to determine the number of OH- moles that have dissolved into an aqueous saturated solution in equilibrium for hydroxides Mg(OH)2, Ca(OH)2, and Sr(OH)2. Three titrations were done for each metal hydroxide of volume 50mL, 1.0mL, and 0.5mL respectively. To find the solubility (Ksp), the concentration of the cation and hydroxide should be known according to this equation: Ksp = [Ion2+][OH-]2 To find the cation concentration, we can calculate the number of moles of OH- that is available in the solution with this relationship: () ( ) ( ) Since we know the concentration of HCl that was used in the trials was 0.002M and the volumes used in the trials, we can use the C=n/V equation to calculate the number of OH- neutralized when the phenolphthalein reached its endpoint. With the following example equation you can see the relationship between the H+, OH-, and the cations: ( ) ( ) ( ) ( ) ()

The ratio is 2:1 HCl to Ca2+, the number of moles calculated for HCl that were neutralized is equal to twice the number of cations that should be dissolved in the solution. Dividing by the amount of H+ or OH- moles by half should give the number of ions dissolved, and dividing that amount again by the amount of saturated solution used for titration should give the ion concentration. The ion concentration is the solubility constant for the Ksp equation which can be simplified to 4(x)3 as x stands for the concentration of the ion. The Ksp values for each metal hydroxide obtained experimentally are 2.7x10-11, 1.4x10-6, and 7.3x10-8 respectively. They show a trend of increasing solubility from Mg(OH)2 to Ca(OH)2 but it decreases again with Sr(OH)2. The literature values are 1.8x10-11 for Mg(OH)2, 5.5x10-6 for Ca(OH)2, and 6.4x10-3 for Sr(OH)2 stating that the value obtained for Sr(OH)2 is incorrect while the others are similar in degree. Theoretically the solubility should increase down the periodic table for Group II elements because as the metals atomic radii increases, the distance from the core increases and they have less force holding them connected to the hydroxide. It also requires less energy to pull apart the ions and less energy is released when the cations bind to water, lowering the activation energy of escape. Hydroxide is a small anion so it is increasingly easier to pull apart the salt hydroxides as the atomic distances increase. Therefore, the Sr(OH)2 should be the most soluble.3 Causes for this error may be that the Sr(OH)2 wasnt actually saturated to its equilibrium amount in the experiment samples. The dilution of Sr(OH)2 may have not been diluted correctly to 5mL Sr(OH)2 to 5mL water before 1mL of that 1:1 solution was taken and diluted again with 50mL of water. The extraction of the 1mL may have taken less Sr(OH)2 moles by chance. The reading and recording of the HCl values may have been skewed or we passed the end-point by adding too much HCl. Phenolphthalein is also a weak acid so adding too much could have occupied some of the OH- and varied the valuables a bit like second Ca(OH)2 trial.

Questions 1. Since the trend for Group II Hydroxides going down the periodic table is to become more soluble, it would mean more OH- ions are dissolved in the aqueous saturated solutions. Since the burette only has about 25mL of volume, the amount of HCl it can titrate at one time is severely limited. Repetitive titrations with a lot of HCl will have to happen to neutralize 50mL
3

http://www.chemguide.co.uk/inorganic/group2/problems.html

of calcium hydroxide and strontium hydroxide each time since they dissociate the best. 2. Based on my results, Beryllium hydroxide should be the least soluble, even lower than Magnesium hydroxide in an aqueous solution with a very low HCl volume required for titration. Barium hydroxide should be the most soluble because it is lower on the periodic table and as the atomic radii increases, the repulsive forces become greater decreasing the lattice energy. 3. a) ( )
( ) ( ) ( ) ()

b) Ca2+ c) HCl d) Phenolphthalein needs to be added to the titrant solution to indicate whether the Ca(OH)2 base has become neutralized and mark the end-point of the neutralization. e) You know when the titration is over when the pink, transparent solution becomes clear and colourless.