CHAPTER 6 COPPER

6.1 Objective (1) Preparation of complexs compound [Cu(NH3)4]SO4 from the starting material of copper (II) sulfate pentahidrate compound; (2) Preparation and identification of khelate complexs compound K2[Cu(C2O4)2] from complex compound of [Cu(NH3)4]SO4; (3) Preparation and identification of double salt K2[Cu(C2O4)2] from the starting material of copper (II) sulfate pentahidrate compound; (4) Preparation and identification of copper metal, copper (I) chloride, copper (II) chloride, copper (II) chloride from product of (2) and (3) above and then become copper (II) sulphate pentahidrate again in a close cycle experiment that efficience and environment friendly.

6.2 Basic Theory 6.2.1 Characteristic of Copper Tembaga In nature copper (Cu) is generally obtained from the ore such as copper pyrite (CuFeS2) and copper glance (Cu2S). Copper has the electron configuration [Ar] 3d104s1. Chemical properties of copper is closely associated with the ionization energy, especially the first ionization energy 745 kJ/mol and the second ionization energy 1956 kJ/mol; heat of atomization of energy and hydration is relatively low i.e. - 2240 kJ/mol for Cu2+ and - 481 kJ/mol for Cu+; positive electrode potential and generally have a low reactivity (Greenwood, 1997). Copper has a single s electron outside the filled 3d skin. This is somewhat less common with a group stoichiometric alkali except in the formal oxidation state +1. d-filled skin is much less effective than the noble gases in protecting the skin s electrons from nuclear charge, so the first ionizing potential of Cu is higher than the alkali group. Because the electrons in the d skin is also involved in metal bonding, then the heat sublimation and melting point of copper is much higher than alkaline

Copper is used in alloys such as brass and can be dissolved in it both in gold. Oxidized copper is very slow and occurs only at the surface in the moist air, and often give the green layer of hidrokso hidrokso carbonate and sulfate (from CO2 and SO2 in the air).

Nitrate acid soluble copper and sulfuric acid in the presence of oxygen. Copper dissolves in nitric acid produces copper (II) wherein nitrate acid as an oxidant. Copper is also soluble in KCN or in solution amionia in the presence of oxygen, which is indicated by the potential (Sudria, 2002).
-0,12V -0,01V
+

Cu + 2 NH3

[Cu(NH3)2]

[Cu(NH3)4]2+

Copper compounds are generally toxic to most living things, so many of them are used as insecticides, fungicides and algisida. Examples are compounds of copper (II) sulfate, CuSO4. Copper (II) sulfate is commercially prepared by oxidizing copper metal with H2SO4 (Cotton, 1989). 2 Cu + 2 H2SO4 2 CuSO4 + 2 H2O Or oxidize the copper (II) sulfide in the air, according to the following reaction. 2 CuS + 2 O2 CuSO4 2.2 Senyawa Kompleks Tembaga Copper compounds are generally toxic to most living things, so many of them are used as insecticides, fungicides and algisida. Examples are compounds of copper (II) sulfate, CuSO4. Copper (II) sulfate is commercially prepared by oxidizing copper metal with H2SO4 (Cotton, 1989). Ions and simple inorganic molecules such as NH3, CN-, Cl-, H2O forming ligand monodentat, i.e. an ion or molecule occupies one of the available space around the central ion in the coordination sphere. Ligands containing two or more atoms, each of which simultaneously form a bond of two electron donor to the same metal ion are called ligands polidentate. These ligands also called chelate ligands. One of the complexes generated in these experiments is the ion tetraaminacuprate (II).

In the wake formula, ion tetraamine cuprate (II) arrows indicate that a pair of electrons donated by each of the nitrogen ions to copper ions. Charge of a complex ion is the charge on the ions that make up the complex, for example: Cu2+ + 4 CN- [ Cu (CN)4 ]2+ If electrically neutral molecules are involved as ligands in complex form, the charge on the ion complex remains the same as the charge on the central atom, for example: Cu2+ + 4 NH3 [ Cu (NH3)4 ]2+ Complex formation can be observed from the color change in solution (Gould, 1995). Cu2+ + 4 NH3 [ Cu (NH3)4 ]2+
blue dark

blue

In aqueous solution, almost all the salt copper (II) is blue, the color characteristics of ion coordination complex 6, [Cu(H2O)6]2+ except the famous copper (II) chloride is greenish because of the complex ion [CuCl4]2- which has tetrahedral geometry or a square base cations depends on their partner. In dilute solutions it becomes blue because displacement Cl- ligand by the ligand H2O. Therefore, if green color to be maintained, in concentrated solution CuCl2 in water was added Cl- ions by addition of solid NaCl or concentrated HCl or gaseous [CuCl4]2-(aq) + 6 H2O (l)
green

[Cu(H2O)6]2+(aq) + 4 Cl-(aq)
blue

If a solution of ammonia is added to a solution of Cu 2 + ions, the solution turns blue to dark blue because there are displacement water ligands by ammonia ligands according to the following reaction. [Cu(H2O)6]2+(aq) + 5 NH3 [Cu(NH3)(4-5)(H2O)(2-1)]2+ + 5 H2O(l)
blue dark blue

The addition of hydroxide ions in a solution of copper (II) sulfate (0.1 to 0.5 M) in droping with velocity~1 mL/min resulted in a light blue gelatinous precipitate salts of copper (II) hydroxy sulfate, [CuSO4.(OH)]2 instead of Cu(OH)2 according to equation below, (Greenwood, 1997): [Cu(H2O)6]2+(aq) + SO42-(aq) + OH-(aq) [CuSO4.nCu(OH)]2(s) + H2O(l)
pale blue

Ions of copper (I) when reacted with chloride ions immediately form a colorless complex ion dichlorocuprate (I), [CuCl2]-. Phase reaction is thought to take place very quickly thus causing the first reaction stage as follows: Cu(s) + H3O+(aq) Cu+(aq) + 2Cl-(aq) Cu+(aq) + H2(g) + 2H2O [CuCl2]-(aq)

If the solution is poured into the air-free distilled water, obtained a white precipitate of copper (I) chloride according to the equation: [CuCl2]-(aq) CuCl(s) + Cl-(aq) In organic chemistry, dichlorocuprate (I), [CuCl2]- used to convert benzene into chlorobenzene diazonium chloride according to the Sandmeyer reaction: [C6H5N2]+Cl-(aq) (copper vitriol), namely: C6H5Cl(l) + N2(g)

There are five copper chemical reactions involving copper (II) sulfate

If the experiments are designed in a closed chain, the copper vitriol would be much less necessary and wastes can also be minimized. The circle closed on the chemistry of copper chain can be described as follows.

NH3 CuSO4 H2SO4 KOCN KCu(OCN)3 [Cu(NH3)4]SO4 K2C2O4 sisa sisa + sisa

K2[Cu(C2O4)2] T

+ sisa

HCl CuO CuCl2

NaOH

CuO + K2CO3 HCl

CuCl2 O2 HCl O2 sisa CuCl Cu CuCl2 + KCl Fe

6.3.1 Chemical and Chemical Aparatus 6.3.1 Chemical Aparatus No. Name 1 Stiring road Size Amount 2 pieces Information Made of heat resistant glass. Used for stirring the liquid in the beaker and also used to help when the pouring /

decantating liquid

in the

filtering process process. 2 Burette 25 mL 1 piece The form like ribbed glass tube and has a faucet at the end. Size ranging from 5 and 10 mL (microburet) with scale 0.01 mL, and 25 and 50 mL with 0.05 ml scale. Serves to remove the solution with a given volume, usually used for titration. 3 Porcelain dish 1 piece Made of porcelain and used to evaporate the solution. 4 Funnel 1 piece Made of heat resistant plastic or glass and has a shape like a stemmed glass, consisting of a funnel with a long stalk and short. How to use it by putting a filter paper into the funnel. The funnel serves to filter the chemical mixture with gravity. Moreover, it also used to assist at the liquid container entering with a into a

narrow

mouth, like a bottle, flask, burette and so on.

Funnel Buchner

1 piece

Essentially the form like funnels and large-diameter

porous. Made of porcelain, plastic or glass. Useful for filtering the sample to dry faster. How to use it by putting a filter paper whose diameter is equal to the diameter of the funnel. 6 Desiccator 1 piece The form like Stackable pot filled the bottom two material dryers, with a removable hard cover in the cold

because it is coated with Vaseline. kinds and There are two

desiccator: vacuum

ordinary desiccator.

Vacuum desiccator on the lid there is a valve that can open the lid, which is connected by hose to the pump. Materials commonly used dryer is

silica gel. Serves as a place to store the samples must be free of water, and dried solids. How to use it is to open the desiccator lid by sliding it sideways, then

place the sample and close the same way.

Silica gel absorbs moisture can still be blue; if the silica gel has turned pink then

heated

in

an

oven

temperature to 105 C until the blue color. 7 Beaker glass 100 250 ml ml; 1 piece The form like a tall glass, with a scale large diameter along the walls. Made of borosilicate glass is resistant to heat to a temperature of 200oC. Used to measure the volume of solution that does not require a high level of accuracy, to accommodate chemicals, heating the liquid, the liquid heating medium. This tool is not a measuring device (although there is a scale, but the error large enough). Used to place the solution and can also for heating chemical solutions. To evaporate the solvent / solvent or to concentrate. 8 Graduated Silinder 25, 50,100, 1 piece glass 250 mL. The form like a tall glass with a scale along the walls. Made of glass or plastic that can not stand the heat, so this tool should not be used to measure the solution / solvent in hot conditions. Size

ranging from 10 mL to 2 L. Serves to measure the

volume of the solution does not require a high level of accuracy in a certain amount. 9 Erlemeyer Flask 25, 50, 100 1 piece mL The form like glass whose diameter gets smaller

growing up with a scale along the walls. Size ranging from 10 mL to 2 L. Alt serves to store and heat the filtrate solution to

accommodate

screening

results, accommodate titrant (the solution is titrated) in the titration process. This tool is not the gauges, although there is a scale on the glass tool (erratum large enough). 10 Wacth glass 3 piece Made of clear of glass, various

consisting

diameter sizes. Serves as a cover while heating the

sample beaker, place when weighing chemicals, and a place to dry solids in a desiccator. 11 Indicator pH paper as needed The form like strips which serves to identify the acidity of the solution In / the other box

substances.

(container) containing a pH indicator paper scale degrees

of acidity (pH) 0-14. 12 Lakmus paper as needed It is an indicator of the form of small sheets of paper, colored red and blue.

Another indicator that there is a liquid mass indicator Phenolphtalein (PP), methyl orange (MO), and so on. Is a tool to measure or determine the level of acidity (pH) solution. 13 Filter paper as needed Paper used to filter the solution. 14 Klem Burett 1 piece Made of iron or steel to hold the burette used for titration. 15 Stirer magnetik 1 piece Magnets are used to stir the solution. 16 Analitical Balance 1 piece Used to weigh solid

chemicals. 17 Magnetic heater 1 piece Square shape, which is used to heat a substance. 18 Test tube holder Square-shaped jaw. Spring polished nickel with a

diameter: 10 -25 mm. Tube clamp serves to clamp the test tube. 19 Volumetric pipette 5 mL 1 piece Use to take the solution with appropriate volume with a label printed on the bubble (goiter) in the middle of the pipette. Use propipet or

10

pipette pump to suck up the solution. 20 Drop pipette 3 piece The form like a small pipe made of plastic or glass with a tapered bottom end and upper end is covered rubber. Useful for taking liquids in small-scale droplets. 22 Statif 1 piece Made of iron or steel that serves to enforce the burette, funnels, separating funnel

and other glassware when used. 23 Spatula 2 piece The form like a long spoon with a flat upper end, made of stainless steel or

aluminum. Serves to take the chemical form of solids, and can be used to stir the solution. 24 Termometer 0-1000C 1 piece Serves to measure the

temperature of the solution or other substances.

6.3.2 Chemical No. Name Chemical 1 Aquades as needed Liquid, colorless, are polar. Used as a of Concentration Amount Information

universal solvent. 2 CuSO4.5H2O as needed The form like solid

11

blue,

used

as in

an the

ingredient preparation of

[Cu(NH3)4] SO4.H2O.

Ethanol

30 mL

Liquid, colorless, and is soluble in water. Used as a nonpolar medium in tetraamin formation of complex compounds of copper (II) sulfate.

HCl

as needed

The state is steamy liquid, colorless, foulsmelling. Used as a titrant for titrating

tetraamin copper (II) sulfate to determine the concentration of NH3. 5 HNO3 as needed Liquid, steaming,

colorless to yellowish. Fumes are very harmful to the eyes. 6 H2O2 30% as needed Liquid is colorless

liquid harmful to the eye. Serves as a

powerful oxidizer, the concentration of 27-

70% or above 70% is very irritating to the skin explode. and easily

12

H2SO4

50% concentrated

and as needed

It

is

highly form

acidic, and is

liquid

corrosive to metals and as an oxidizer. 8 I2 as needed The form like purplish black solids, soluble in water, but easily

soluble in KI, easily sublimes. 9 K2C2O4.H2O 8 gram Are solid, crystalline form, pungent, brittleness exposed nails is colorless, causing when cause

irritation of the mucous membranes, esophagus, and tract. 10 KI as needed The form like a white solid. Used as a solvent to dissolve the I2. 11 Na2CO3.H2O as needed Are solid, crystalline or white powder form. gastrointestinal

Serves to produce CO2. 12 NaOH 30% as needed Are solid, the form of white flakes. Both the solid and the liquid is corrosive. 13 Na2SO3(aq) 0,1 M 8,3 mL As a titrant for the iodometric titration and the detection of excess

13

I2 in the determination of concentration. 14 NH3 Concentrated 20 mL The state is colorless gas, is irritating to eyes and skin. Used as a solution that will react with CuSO4.5H2O copper

forming Cu(OH)2.

14

6.4 Procedure and Observation Result No. Procedure Theoritically Observation Experiment Result

5.1 Preparation of [Cu(NH3)4]SO4 . H2O 1. CuSO4.5H2O 5 grams In aqueous solution, almost all the salts of copper (II) CuSO4.5H2O is blue crystal, the mass is 5.0184 grams.

dissolved in 10 ml aquades ions are blue that form a complex coordination of 6, which has been heated in [Cu(H2O)6]2+ : advance and reheat until all the copper (II) sulfate CuSO4.5H2O + H2O [Cu(H2O)6]2+ + SO42When a solution of ammonia in very little happening deep blue color, which is caused by the formation of complex ions tetraaminocuprate (II): Cu(H2O)6]2+ + 2NH3 + SO42-

pentahydrate dissolved.

When CuSO4.5H2O dissolved in hot aquades, not all soluble. When heated with stirring, the crystals

Cu(OH)2.CuSO4 + 2NH4+ + 10H2O If the solution containing ammonium salt (or the solution is very acid and ammonia used to neutralize it 2. Added 20 ml of very much), the precipitation did not occur at all, but the blue color is formed immediately.

dissolve in water and produce a blue colored solution. Ammonia solution is clear and pungent. After the solution was added 20 mL of concentrated ammonia, the precipitate formed on the bottom of Erlenmeyer.

concentrated solution

ammonia

(Cu(OH)2 Cu(OH)2.CuSO4 + 8 NH3 + H2O 2[Cu(NH3)4]2+ + Dark blue precipitate will be formed SO42- + 2OH-

15

but will dissolve again) and stir until the solution The overall reaction is: 2[Cu(H2O)6]2+ +10NH3 2[Cu(NH3)4(H2O)]2+ + NH4+ + 2OH- + 9H2O

After stirring, the precipitate dissolves and the resulting dark blue solution, as follows

becomes clear dark blue.

3.

While stirring gently, pour the clear solution into a dark blue in 30 ml of ethanol. Let stand for 15 minutes until crystals

Ethanol is a colorless clear liquid. After a dark blue solution mixed with ethanol, is formed dark blue precipitate and blue solution.

16

formed. 4. The blue crystals After 15 minutes the precipitate separated by using Buchner funnel. After the filtration process is formed a dark blue) precipitate of [Cu(NH3)4SO4] on filter paper and the filtrate is clear blue. While the crystals filtered is dark blue.

precipitated were filtered by using Buchner funnel. Wash the crystals three times, each with 5 ml of ethanol. Breathe the air for 10 minutes so the crystals are completely dry. 5. The was remaining evaporated reaction in a

Filtrate screening results are clear blue heated until the volume just a few mL. Solution is then poured by concentrated H2SO4 and dark blue colors are disappear and then formed light blue solution. The crystals obtained are 5.4003 grams.

vacuum or heating until the volume is only a few mL, then concentrated sulfuric acid dropwise until the blue Then color the disappeared. solution was

stored for processing at substrate 4. 5.2 Preparation of K2[Cu(C2O4)2]SO4 .2H2O 17

1.

K2C2O4.H2O dissolved in

16 a

grams Tetraamine complex compounds of copper (II) sulphate K2C2O4.H2O compound is white crystal. warm is dark blue can be isolated and treated with potassium to produce potassium chelate complex

aquades, then poured into a oxalate

solution made of 5 grams compounds oxalato cuprate Turkey blue. Reaction as of [Cu(NH3)4]SO4 . H2O in follows: 12 ml aquades. Dropwise a concentrated sulfuric acid until the color is dark blue [Cu(NH3)4(H2O)]SO4+2K2CO4.H2O K2[Cu(C2O4)2].2H2O + K2SO4 + NH3 The mass of K2C2O4.H2O is 8.0085 gram, and then dissolved in 50 mL aquades.

turned to blue turkey. (pH The addition of concentrated sulfuric acid solution range 4-6)

makes the solution changes the color from dark blue to [Cu(NH3)4]SO4.H2O compound is dark blue powder blue Turkish, is caused by reaction between the compounds tetraamine copper (II) sulfate with sulfuric The mass of [Cu(NH3)4]SO4.H2O used is 2,5050 gram, and then dissolved in 6 mL acid. Reaction as follows: aquades, it formed dark blue solution. [Cu(NH3)4(H2O)] + 2(NH4)2SO4 The addition of sulfuric acid will cause protons will join with NH3 to form NH4+ and ammonia complex will be damaged. Ammonia molecules displaced by H+ is more acidic than Cu2+. Then the water molecule will replace the NH3 to form [Cu(H2O)4]2+. The reasons not to use HCl because HCl can react with [Cu(H2O)4]2+ forming K2C2O4 clear solution was added to [Cu(NH3)4]SO4 solution dark formed blue 18
2+

+ 3H2O + 2H2SO4 [Cu(H2O)4]

2+

[CuCl4]2+. However, [Cu(H2O)4]2+ will never be intermediate species such as [CuCl(H2O)3]+,

dark blue solution.

completely converted into [CuCl4]2+, because there is an After the droped by concentrated H2SO4, the solution becomes blue turkey, then the solution was tested byuniversal indicator. The pH is 6. [CuCl2(H2O)2], and [CuCl3(H2O)]-.

2.

The mixture was placed in an ice bath for at least 1 hour or overnight in

Once placed in ice bath for 1 hour are formed turkey blue crystals and clear solution.

refrigerator.

19

3.

Turkish

blue

crystals

Crystal decantated and the filtrate cooled again in ice bath. The crystals which formed were washed by cold aquades 3 times. The crystals that have been washed are placed in a desiccator so that the crystals formed are completely dry. Further crystals obtained were weighed and the weight of crystal is 5.4003 grams.

formed in the decantation, then washed several times by ice water. 4. The crystals are dried in a desiccator containing blue gel. Observed morphology of the crystals formed. The remaining reactions are

stored for use at sub. 4. 5.3 Pyrolysis of K2[Cu(C2O4)2]SO4.H2O 1. The entire preparation of Chelate compounds of potassium oxalato cuprate that is The isolation product is blue crystal. isolation products in the blue Turkey color, if perfectly pyrolyzed will produce The heating is conducted on the heater. substrate 2 placed in a copper (II) oxide, potash (potassium carbonate), carbon After melted, the mixture is black. porcelain dish and heat on dioxide, and water. As for the reaction: the Bunsen burner. Melting will begin from the edge of the cup toward the middle. K2[Cu(C2O4)2] .H2O + CO2 + 2CO(g)

2H2O(g)+ K2CO3 + CuO

20

2.

If

all

the

preparations

After a heated at long time, all isolation products turn black resembling sand.

melted, keep the Bunsen burner. Then allowed to cool at room temperature.

21

3.

Changes observed and the results weighed. of pyrolysis

The color of products obtained is grayish black and the weight is 3.0831 grams. Produk yang diperoleh berwarna hitam keabu-abuan dan beratnya sebesar 3.0831 grams.

5.4 Acquisition of Copper Metal by Cementation 1. The result of pyrolysis in substrate 3 was mixed with 20 mL of half concentrated of hydrochloric acid into a beaker glass. Cu2+(aq) + Fe(s) Cu(s) + Fe2+(aq) The reaction that occurs in this procedure are as When the pyrolysis was added by half follows: K2CO3(s)+CO2(g)+ 4HCl(aq) CuCl2(aq) + 2 KCl(aq)
hijau tua

concentrated HCl, the mixture becomes light green and there are air bubbles.

2.

The mixture was heated briefly to produce a dark

The mixture is heated and formed dark green solution.

22

green solution.

3.

This solution is integrated with the rest of the reaction in the sub 1 and 2 (the pH range of the mixture is 13).

The rest of reaction 1 = colorless The rest of reaction 2 = blue light When the rest of the reactions 1 and 2 are mixed with earlier solution, the mixture remained dark green where the degree of acidity (pH) = 1.

23

4.

Within 30 minutes, added 2.25 gram of fine iron powder stirring. gradually while

Iron powder is blackish gray color.

The mass of iron powder used is 1.1251 grams. After added iron powder, red-brown

precipitate is formed, while the color of the solution changed from dark green to pale green, then becomes turbid green, and finally become white turbid. 5. Added dropwise of When concentrated HCl is added, the mixture remained red-brown precipitate, and white turbid solution.

concentrated hydrochloric acid to maintain pH 1-3

24

(using a pH meter to measure the pH of the solution), briefly. 6. The mixture is decantated to separate the brown-red precipitate of copper then heated

The degree of acidity (pH) of this mixture is 1.

After decantation I, gained filtrate I that is yellowish clear. The precipitate of decantation is red brown color. After heated and added concentrated HCl, the solution is yellow and still there is red-brown precipitate. Filtrate of decantation II is yellow. After the filtrate I and II put together, forming yellow solution. The filtrate was added by 0.2507 grams of iron. The filtrate was added by iron powder is formed red precipitate. Red precipitate after decantation and

formed. The precipitate is heated once again with a little hydrochloric concentrated acid (iron

must all exist in solution). Decantation once again and the united filtrate available. 7. Added 0.25 gram of iron powder into the filtrate which had been unified. If there is still copper

cementate, do decantation and repeat the step number

concentrated HCl is added to form a yellow

25

6 until all the copper cementated (no precipitate again).

filtrate. When the yellow filtrate combined with the filtrate I and II is form a mixture of greenish yellow. The precipitate is red-brown and the mass is 0.9574 gram.

8.

Deposition cementation

of

copper are

results

collected and dried. After dried, it is weighed.

To ensure that there is no Fe in the precipitate, the precipitate washed again by half concentrated HCl. After the washing process, the mass of precipitate was reduced to 0.7075 grams.

26

mol =

0,7075 0,01 mol 63,53

9.

The

residual

filtrate

The filtrate is stored for use in iron chemistry experiments.

containing iron ions are stored for use at the trial preparation of Fe(acac)3 on the iron chemistry topics. 5.5 Preparation of CuCl 1. CuCl2 solution of substrate The reaction that occured in this step is: 6 was heated in beaker glass to remove dissolved oxygen gas. 2HCl + Na2CO3 2 NaCl + CO2(g) + H2O [CuCl4]2- + 6 H2O [Cu(H2O)6]2+(aq)+ 4 Cl-

Solution of substrate 6 is heated and obtained bright green solution as well as gas bubbles arise..

[CuCl4]2- + Cu 2 [CuCl2][CuCl2]- CuCl + Cl-

2.

Dropped the solution of concentrated hydrochloric

To the solution is etched by the concentrated HCl slowly and its pH is obtained 1.

27

acid slowly into a solution of CuCl2 until the pH reached 1-3. 3. Added soda (sodium At the time of adding soda to the solution that arise gas bubbles occur more (much CO2 protective atmosphere)

carbonate) to the solution of the tip of spatula to produce CO2 of protective atmospheric. 4. All the copper powder produced in the substrate 4 added to the solution, then slowly stirred while heated for 30-35 minutes. 5. Added (if needed) a little soda and hydrochloric acid to maintain pH 1-3 and to maintain protective the CO2

Copper powder on the substrate 4 is added to the solution and stirred slowly and heated for 35 minutes and obtained the solution is greenish brown.

After added by soda and HCl, the solution is become blackish green (hijau lumut).

atmosphere.

Beaker glass covered by

28

watch glass. 6. During heating, evaporate 75 mL of water from the solution, then cool the rest of the solution
o

After heated, cooled and added H2SO4 formed yellow solution and not obtained precipitate yet.

at

temperature of 0 C and added 3 mL of sulfuric acid (to stabilize the CuCl from oxidation by oxygen in air). 7. The solution is filtered in ice water (it will separate the insoluble CuCl from a solution of [CuCl2] ) and decantation precipitate white formed
-

After cooled is formed green solution and there are precipitate. Further decantation is obtained pale yellow precipitate and light green filtrate. After the precipitate was washed by ethanol is obtained white precipitate.

immediately, then wash the precipitate by little ethanol. The solid obtained was dried in the desiccator.

29

8.

If the rest of the solution is colorless, throw down the sink. If it still blue, it means that it still contains Cu2+ ions and need to be addressed further. Blue

The blue filtrate is stored for the next step.

solution was stored for further processing at

substrate 8. 5.8 Re-production to Produce Vitriol Copper 1. The entire preparation of The reaction that occured in this step is: CuCl results in substrate 7 2 CuCl 2 HCl + 1/2O2 CuCl2 + H2O + Clis placed in the open air 2CuCl + H2O2 + 2HCl 2CuCl2 + 2H2O until the color is green, CuCl2 + NaOH + Na2CO3 CuO + CO2 + NaCl + then suspended with 20 mL H2O of dilute hydrochloric acid. CuO + H2SO4 CuSO4 + H2O The suspension was put together with the remaining blue solution at substrate 7. These mixture then flows After placed in the open place, the white precipitate of CuCl that is preparation results is turned to green and after the addition of dilute HCl is form green suspension. When the suspension combined with the residual filtrate and flowed by oxygen gas, the color of the solution is become lighter.

30

through the oxygen gas until the solution become bright green. 2. Added a few drops of 30% hydrogen peroxide into the mixture. Then added After added H2O2 30%, the solution is remained bright blue. When NaOH solution was added is arise black precipitate, but immediately

dropwise the solution of 30% sodium hydroxide to pH range is 4-5. 3. Heat the solution with a small flame, and then

disappeared and the pH = 5

After the addition of Na2CO3 powder until the pH = 11, is formed a brown solution. After heated, from the brown is arising black precipitate of CuO. Then filtered, obtained black precipitate and a colorless filtrate.

added by little powdered of Na2CO3 solution until the pH reached 11-12. By the heating the precipitate will form black CuO. The

precipitate which formed was filtered and washed by aquades. Colorless filtrate can be discarded into

31

landfills for the remaining solution halogen. 4. Black precipitate of CuO is inserted in beaker glass, then added dropwise 50% sulfuric acid solution until the precipitate of CuO still a little and decantation immediately. 5. The solution is cooled at room temperature resulting the crystallization process. To enhance crystallization, place the solution in a refrigerator overnight. 6. Crystals formed and the remaining solution is Obtained crystals and blue filtrate. After cooling for 1 week blue crystals is formed. At the time the black precipitate of CuO was added by H2SO4 50% is formed blue solution. When the precipitate is still a little, soon decantation. containing

decantation. The crystals are washed by ice water 32

and

filtered.

Then

the

crystals are dried in a desiccator.

7.

Copper vitriol crystals that formed were weighed and compared with copper

The crystal vitriol copper obtained is 0.1017 grams.

vitriol that has been used in this experiment cycle. 8. If the residual solution still contains copper ions, the remaining stored. solution is The remaining filtrate obtained is very little and stored for recycling.

33

6.5 Discussion 6.5.1 Preparation of [Cu(NH3)4]SO4 In this cyclical chemical copper experiment, was used compound of copper (II) sulfate anhydrous starting material as much as 5.0184 gram. CuSO4.5H2O compounds are difficult to dissolve in aquades at normal and low temperatures, so aquades that is used to dissolve the compound of copper (II) sulfate anhydrous must be heated first. To enhance dissolution of copper (II) sulfate anhydrous in aquades, then the mixture was stirred while heated in an electric heater. The solution is then added to 20 mL of concentrated ammonia. At the beginning of the addition, then the precipitate formed after all of concentrated ammonia is added to a solution of CuSO4, the precipitate was dissolved again. The precipitate that had formed before the deposition of the Cu(OH)2. At the dissolution of CuSO4.5H2O is occurred reaction as follow :
H2O

CuSO4 . 5 H2O(s)

CuSO4 (aq)

When CuSO4 solution was added by concentrated ammonia is occurred reaction as follow: CuSO4 (aq) + NH4OH Cu(OH)2 (s) + (NH4)2SO4 The precipitate Cu(OH)2 which is formed is not stable, so it can be dissolved again. The addition of ammonia can shift the equilibrium, which causes the formation of complexes [Cu (NH3)4]SO4 with the following reaction. CuSO4 (aq) + 4NH3 (aq) [Cu(NH3)4]SO4 (aq) After stirring was stopped formed clear dark blue solution. At the time of adding concentrated ammonia is still being done in hot conditions, in order to complete dissolution occurred (no sediment). Complex solution which has been obtained is then poured into the Erlenmeyer flask containing 30 mL of ethanol. The reasons complex solution was dissolved into ethanol because a complex compound is not soluble in nonpolar solvents, namely ethanol, so it can form complexes precipitate tetraamin copper (II) sulfate, [Cu(NH3)4]SO4 (s) which is the color is blue If the solvent that is used is not nonpolar solvent but polar solvent then it can lead to the formation of ammonium sulfate. This situation can occur because it is caused by the

34

positively charged ammonium and negatively charged of sulfate, so that when joined will form a compound of ammonium sulfate. A mixture of precipitate [Cu(NH3)4]SO4 with its solution then allowed to stand for 15 minutes. This has purpose to be a perfect crystallization. The precipitate then separated using a Buchner funnel. Function using a Buchner funnel in the process is to accelerate the filtering and minimize liquid content in the precipitate. Crystalline precipitate filtered and washed with ethanol which aims to remove contaminants, in order to obtain pure crystals. The result of filtering process (filtrate) was mixed with ethanol washing results. Then evaporated until the volume is only a few mL. It aims to make the ethanol that contained become evaporate. Indicators as a sign that ethanol has evaporated is the color of the filtrate from clear blue to turbid blue. Furthermore, the turbid blue solution was added concentrated sulfuric acid as much as 5 drops, so the solution becomes colorless solution, because the rest of the bases are still present in the complex Cu filtrate has been neutralized by sulfuric acid. Crystalline precipitate obtained dark blue and then dried in an oven. When weighed mass of crystal obtained was 4.4590 grams. Then from this experiment is obtained yields crystal of [Cu(NH3)4]SO4 was calculated as follows:

Mass of CuSO4.5H2O = 5,0184 gram (molar mass = 249,68 g/mol) Mol of CuSO4.5H2O =
5,0184 gram 249 ,68 gram / mol

= 0,02 mol Volume of NH3 = 20 mL (Mr = 17 g/mol) Density of NH3 = 0,91 g/mL mol of NH3 = (20 x 0,91) / 17 = 1,070 mol Mass of [Cu(NH3)4]SO4. H2O theoritically = 4,91 gram that was obtained from calculation process as below:. CuSO4.5H2O m : 0,02 mol + 4 NH3 1,07 mol [Cu(NH3)4]SO4. H2O + 4 H2O 35

b : s :

0,02 mol -

0,08 mol 0,99 mol

0,02 mol 0,02 mol

0,08 mol 0,08 mol

so, mass of [Cu(NH3)4]SO4. H2O

= mol x molar mass = 0,02 mol x 245,5 g/mol = 4,91 gram

In this experiment was obtained 4,3950 gram of [Cu(NH3)4]SO4.H2O, so the percentage yield is : % yield =
mass of exp eriment x 100 % mass theoritically

4,3950 x 100 % 4,91

= 89,51%

6.5.2 Preparation of K2[Cu(C2O4)2]SO4 . 2H2O In the preparation of K2[Cu(C2O4)2]SO4.2H2O used half of the mass that is in substance the procedure, which is 2.5050 grams of [Cu(NH3)4]SO4.H2O dissolved in 6 mL aquades, while the weight of K2C2O4.H2O used as much as 8.0085 which is dissolved in 50 mL aquades. When K2C2O4.H2O dissolved in warm aquades lukewarm, formed a white turbid solution and the K2C2O4.H2O crystal which is difficult soluble in cold aquades, so it needs to be warmed first so that the crystals dissolve completely. Powder of [Cu(NH3)4]SO4. H2O dissolved in aquades produce a dark blue solution. When both solutions are mixed together, formed a dark blue solution. Then the dark blue solution was added by 30 drops of concentrated sulfuric acid, so the color of the solution becomes blue Turkey. The purpose of the addition of sulfuric acid to acidify the solution. When the pH of the solution measured, the pH is 6. The reaction that occurs between the solution of [Cu(NH3)4]SO4.H2O with K2C2O4.H2O solution is as follows. [Cu(NH3)4]SO4. H2O + 2 K2C2O4.H2O K2[Cu(C2O4)2].2 H2O + K2SO4 + NH3

36

Turkish blue solution then was cooled in an ice bath, so that the formation of crystals becomes more optimal. After cooling in an ice bath crystals obtained the blue turkey in a light blue solution. The next step, the crystal was decantated and washed 3 times with cold aquades. The washing process has a purpose to eliminate the impurities that exist in these crystals. The light blue solution as the result of washing was mixed with the filtrate obtained in the process of decantation.

Pale blue color filatrate The filtrate that was obtained still contains complex K2[Cu(C2O4)2]SO4.2H2O, so it must be dried in a desiccator. Mass of crystals were obtained is 5.4003 grams, while the filtrate obtained was stored for the next experiments.

6.5.3 Pirolisis K2[Cu(C2O4)2]SO4. H2O Crystal of K2[Cu(C2O4)2]SO4.H2O that was obtained was placed in a porcelain dish, then heated. After heated, initially blue crystal turned into blackish brown, due to a chemical breaking structure into the gas phase. The black color formed is the color of CuO. Chelate compounds of potassium oksalato cuprat which is has blue Turkey color, if perfectly pyrolyted will produce copper (II) oxide, potash (potassium carbonate), carbon dioxide, and water, such as the following reaction. K2[Cu(C2O4)2] .H2O

2H2O(g) + K2CO3 + CuO + CO2 + 2CO(g)

37

The crystal as the result of pyrolysis was weighed and the mass was obtained is 3,0831 gram.

heated

The result of pyrolysis Crystal of K2[Cu(C2O4)2]SO4. H2O

Color of crystal turns become brown-black

6.5.4 The acquisition of Metals Copper cementation Crystal results of pyrolysis that was obtained with mass 3.0831 grams was added with half-concentrated HCl (6M) produced a green solution. The purpose of the addition of HCl is to react the results of pyrolysis into CuCl2 and KCl. The green color solution is CuCl2. In addition, when the addition of half-concentrated HCl also appear bubbles gas which indicates the formation of CO2. Thus, the addition of HCl was carried out in acid room. As the reaction, are as follows:

CuO(s) + K2CO3 (s) + 4 HCl (aq) CuCl2(s) + 2 KCl + CO2(g) + 2H2O (g) The solution was heated in order to accelerate the reaction and remove the water present in the solution. Once heated, the solution became dark green. The solution of this reaction, then mixed with the rest of the reaction in the sub 1 (colorless solution) and the rest of the reaction sub 2 (blue solution), formed a light blue solution. The mixing is aimed to obtain Cu that may still remain in the previous reaction. When checked the pH of the mixture is 1.

38

Filtrate sub 3.1

Filtrat sub 3.2

The solution after heated

Milk blue solution

In the solution that has been formed, added as much as 1.1251 gram of iron powder. The addition of iron powder done little by little, which aims to iron powder can be dissolved completely in solution. Stirring was done by using a stirring rod, because if done using magnetic Stirrer, iron will stick to the magnetic Stirrer, considering the iron can be drawn by the magnetic field of the magnetic Stirrer. When iron powder was added, the solution formed a yellowish green and brick red precipitate is formed at the base of the beaker. The reaction that occurs when the addition of Fe on copper are as follows. CuCl2(aq) + Fe (s) Cu(s) + Fe2+(aq)

Yellowish green solution and brick red precipitate Yellowish green solution then was heated with a purpose to perfecting the precipitate formed. Furthermore, the precipitate formed was decantated, obtained the brick red precipitate and green solution. Precipitate of brick red was dropped by HCl and heated slightly. The addition of HCl is intended to Fe2+ which is likely still contained in the precipitate of Cu can be dissolved in HCl to form a yellow FeCl2. With the addition of HCl, has purpose to dissolve the iron by produce iron (II) salts and hydrogen gas. Fe + 2H+ Fe2+ + H2 (g)

39

Fe + 2HCl Fe2+ + 2 Cl- + H2 (g) After addition of HCl and heating process, was formed a little yellow FeCl2. All the filtrate obtained was mixed and re-added 0.2507 grams of iron powder until no more copper is formed. Copper precipitate was collected and washed with half concentrated HCl. The reason the use of half-concentrated HCl (not concentrated HCl), because if using concentrated HCl maybe copper can dissolve in HCl. When weighed, was obtained mass of copper precipitate is 0.7079 grams. While the residue of the reactions (green solution) was stored for iron chemistry topic.

The precipitate copper before it is washed with 6M HCl

The residue of the cementation reaction (green solution) The calculation is done using the mass yield of [Cu(NH3)SO4.H2O. Because, in experiments that was conducted on the pyrolysis was not carried out the weighing of the product obtained. Besides that, in pyrolysis was obtained precipitate containing the two products of CuO(s) dan K2CO3(s). 40

Mass of [Cu(NH3)SO4.H2O = 4,91 gram ; Mr = 245,5 g/mol Mol of [Cu(NH3)SO4.H2O = 4,91/245,5 = 0,02 mol Reaction that is occurred is as follow. [Cu(NH3)4]SO4. H2O + 2 Na2C2O4.H2O mol of [Cu(NH3)SO4.H2O = mol Cu so, mass of Cu theoritically = mol Cu x Mr C = 0,02 mol x 63,5 g/mol = 1,27 gram In thos experiment was obtained 0,7079 gram of Cu, so that can be calculated % yield as follows. % yield = = 55,74% = K2[Cu(C2O4)2].2 H2O + K2SO4 + NH3

6.5.5 Preparation of CuCl2 solution CuCl2 compounds in chemistry copper experiment was not made through the preparation of KCu(OCN)3, but was made by dissolving crystals of bright green CuCl2.2H2O in aquades. When the crystals are dissolved in aquades CuCl2.2H2O, was obtained bluish green solution. Preparation of CuCl2 solution is adjusted to the amount of copper obtained. The amount of copper vitriol obtained in this experiment is 1,0215 grams. The calculation is as follows.

Mol Cu

gram Cu Mr Cu

0,7079 0,01 mol 63,5

41

Based on the reaction equation : Cu(s) + CuCl2(aq) 2CuCl So, mol of CuCl2 that is needed is:
mol of K 2 C 2 O 4 coefficien of CuCl 2 x mol Cu coefficien of Cu

1 x 0,01 mol 1 0,01 mol

So, mass of crystal CuCl2.2H2O that is needed: Mass of CuCl2.2H2O = mol x Mr CuCl2.2H2O = 0,01 mol x 170,48 gram/mol = 1,7048 gram So, mass of CuCl2.2H2O that is required is 1.7048 gram and then dissolved in 50 mL aquades. For the next step, this solution was heated and obtained greenish blue solution.

6.5.6 Preparation of CuCl In experiment of preparation of CuCl was used CuCl2 solution. When the CuCl2 solution was heated, bluish-green solution formed. The purpose of heating is to remove oxygen gas which is dissolved in the solution (evaporate into the air), so it does not interfere the next processes. When measured the degree of acidity of the solution, the pH is 1, so do not do the addition of concentrated HCl, because the addition of concentrated HCl has purpose to make the solution becomes acidic conditions (pH = 1). CuCl2 solution that formed was added by a spatula tip of Na2CO3. The addition of Na2CO3 were conducted to form a CO2 protective atmosphere that can prevent the entering of oxygen from the air into the system which can oxidize copper (I) into copper (II). When the addition of sodium carbonate, the gas bubbles formed in the solution. Bubbles is a CO2 protective atmospheric produced from the decomposition of Na2CO3 as follows. Na2CO3 2 Na+(aq) + CO32-(aq)

42

CO32- ions that was formed will further react with Cu+ to produce Cu2CO3 which then reacts with H+ from the addition of HCl to form H2O and CO2. The reaction that is occurres is as follows. 2Cu+ + CO32- Cu2CO3(s) Cu2CO3 + 2H+ 2Cu+ + H2O + CO2(g) Into the solution, then added all the Cu powder produced at the experiment sub 3.4. After the copper powder was added, the solution was then heated for 30-35 minutes. The addition of copper powder led to the solution became brown. Heating is done so that all the powder can be dissolved perfectly or excellent (no sediment Cu powder that has not dissolved). This heating is maintained, to keep warm so that Cu+ has formed no longer be oxidized become Cu2+. The reaction is: Cu2+(aq) + Cu(s) 2 Cu +(aq)

Solution that has been formed, was added by baking soda which is has purpose to form a protective CO2 atmosphere. HCl solution was not added, because its acidity is enough acid (pH 2). Solution had been added the baking soda, then heated and covered with a watch glass. It is intended that no oxygen that goes into the solution, because it can oxidize Cu + to Cu2+ again. During the heating process was evaporated about mL of solution. Evaporation process is intended to keep CuCl2 solution from insistence of Cl- ligands by water ligands according to the following equation. [CuCl4]2- + 6 H2O [Cu(H2O)6]2+(aq) + 4 Cl-

After volume of solution about mL of the initial volume, the green solution was placed in an ice bath and concentrated sulfuric acid was added. The purpose of the addition of H2SO4 is to stabilize the CuCl that was formed from the oxidation by oxygen from the air. After cooling a white precipitate formed and the solution is pale yellow color. The precipitate obtained was separated by decantation. The precipitate obtained is very little, because the copper powder produced in the previous experiments is very little that is 0.7079 grams. The filtrate as the result of the decantation was heated again to make the water evaporated so that the solution will be saturated. This white precipitate is CuCl, which is then 43

washed with a little ethanol and decantated. After decantated and washed with ethanol gained a little white precipitate CuCl which is insoluble in [CuCl2]-. The reaction that occurs is as follows. [CuCl2]- CuCl + ClThe precipitate was dried in a desiccator, while the remaining solution is pale yellow stored for the next experiments.

6.5.7 Recycling To Produce Copper Vitriol The preparation results of CuCl preparation will be recycled to get copper vitriol. The solid CuCl preparation results placed in an open place, so that occurred oxidation process of Cu+ to Cu2+. This is because the presence of oxygen from outside air. Indications of this oxidation process is the change color of CuCl solid from white to green.

Then the solid was suspended with 20 mL of dilute HCl. Next add the rest of the reaction of sub.7, formed a colorless solution older. This solution was then added H2O2 30% as much as 4 drops which aims to enhance the reaction CuCl become CuCl2, (all Cu+ can be oxidized to Cu2+). Here is a reaction that occurs. CuCl + H2O2 CuCl2 + H2O After that, the solution is was heated with a little fire, which is then added powder of sodium carbonate while still heated. With the addition of sodium carbonate, the color of solution turns brown and the gas bubbles formed on the surface of the solution. These gas bubbles are CO2 gas produced from the reaction as follows:

CuCl2(aq) + Na2CO3(s)

CuO(s) + NaCl(aq) + CO2 (g)

The addition of Na2CO3 was done until the pH range 11-12. Therefore, the addition of Na2CO3 into the solution still being done while still heated with a small fire. After some time the addition of Na2CO3, pH of the solution was measured again using a universal indicator and obtained pH = 11 and formed a brown solution. Then the solution was kept heated to 44

make the black precipitate of CuO formed. At this heating, the solution is brown at first, gradually turns into a black and a black precipitate is formed which is precipitated of CuO. Black precipitate then separated by filtering process. The filtrate is colorless, it can be safely removed to a laundry tub. Further precipitatewhich are still left in thefiltering paper washed with aquades to remove the impurities. Black precipitate was transferred to a beaker and added 50% sulfuric acid. The purpose of this is the addition of sulfuric acid to form copper sulfate to the reaction as follows. CuO(s) + H2SO4(aq) CuSO4(aq) + H2O(i) After the sulfuric acid was added, forming a blue solution. Then the solution was cooled in a refrigerator for one week to obtain CuSO4 crystals (copper vitriol).

CuO precipitate after the addition of sulfuric acid (formed blue solution)

The crystals that was obtained in this experiment is 0.1017 grams and the filtrate results of decantation in the form of blue-colored solution. Then the filtrate was stored for next experiment recycling.

6.6 Closing 6.6.1 Discovery

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6.2 Conclusion Based on the observation result and discussion can be concluded that : 1. Complexs compound [Cu(NH3)4].SO4 can be made by reacting CuSO4.5H2O with concentrated NH3 according to the following reaction: CuSO4.5H2O + NH3 [Cu(NH3)4].SO4 + 5 H2O In this experiment was obtained [Cu(NH3)4].SO4 amount 4,4590 gram by percentage yield = 90,81% 2. Complexs K2[Cu(C2O4)2].2 H2O can be made by reacting [Cu(NH3)4].SO4 with K2C2O4 according to the following reaction: [Cu(NH3)4].SO4 .H2O(aq) + K2C2O4(aq) Blue Colorless K2[Cu(C2O4)2].2 H2O Dark Blue

3. Pirolysis of K2[Cu(C2O4)2].2 H2O producing CuO ,K2CO3 and also H2O. 4. Copper can be obtained from cementation process by reacting the result of pyrolysis with HCl 6 M according to the following reaction: CuO (s) + K2CO3 (s) + 4 HCl (aq) CuCl2(s) + 2 KCl(aq) + CO2(g) + 2 H2O (g) Amount 0,7079 gram of Cu was obtained from cementation process, and the percentage yield = 55,74%.

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5. CuCl can be obtained by reacting CuCl2 with HCl producing CuCl according to the following reaction: CuCl2 + Cl- CuCl + Cl2 Then was added by sodium carbonate producing CO2 gas according to the following reaction. 2 Cu2+ + CO32- Cu2CO3 Cu2CO3 + 2 H+ 2 Cu2+ + H2O + CO2 After that was added by Cu powder from procedure 4, is occurred reaction as follow: 2 Cu2+(aq) + Cu(s) 2 Cu+(aq) [CuCl4]2- + 6 H2O [CuCl2]- CuCl + ClFrom the reaction was otained white crystal of CuCl 6. Recycling of copper vitriol was done by reacting CuCl2 with Na2CO3 produce CuO which is reacted with H2SO4 produces CuSO4. In this experiment was obtained as much as 0.1017 gram of copper vitriol. [Cu(H2O)6]2+(aq) + 4 Cl-

6.3 Suggestion

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48