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EXPERIMENT VI

ELEMENTAL CHEMISTRY
Mei 9th 2017

A. Objectives
1. Learn how to prepare halogen
2. Study some properties of chlorine, bromine, and iodine
3. Study some complex ions

B. Introduction
The Group VIIA elements, called the halogens, have very similar properties, or at least
they have properties that change smoothly in progressing down the column. All are reactive
nonmetals, except perhaps for astatine, whose chemistry is not well known. As a second-period
element, fluorine does exhibit some differences from the other elements of Group VIIA, although
these are not so pronounced as those of the second-period elements in Groups IIIA to VIA. The
solubilities of the fluorides in water, for example, are often quite different from those of the
chlorides, bromides, and iodides. Calcium chloride, bromide, and iodide are very soluble in water.
Calcium fluoride, however, is insoluble. Silver chloride, bromide, and iodide are insoluble, but
silver fluoride is soluble.
All of the halogens form stable compounds in which the element is in the -1 oxidation
state. In fluorine compounds, this is the only oxidation state. Chlorine, bromine, and iodine also
have compounds in which the halogen is in one of the positive oxidation states -1, -3, -5, or -7.
The higher positive oxidation states (>+1) are due to the involvement of d orbitals in
bonding.(Ebbing and Gammon, 2009)
Transition metals are defined as those elements that have (or readily form) partially filled d
orbitals. As shown in Figure 19.2, the d-block elements in groups 3–11 are transition elements.
The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet
this criterion because the d orbital is partially occupied before the f orbitals. The d orbitals fill
with the copper family (group 11); for this reason, the next family (group 12) are technically not
transition elements. However, the group 12 elements do display some of the same chemical
properties and are commonly included in discussions of transition metals. Some chemists do treat
the group 12 elements as transition metals. (Rice University, 2015 : 1078)

The transition elements have many properties in common with other metals. They are
almost all hard, high-melting solids that conduct heat and electricity well. They readily form
alloys and lose electrons to form stable cations. In addition,transition metals formawide variety of
stable coordination compounds, in which the central etalatomor ion acts as a Lewis acid and
acceptsoneor more pair sofelectrons. Many different molecules and ions can donatelone pairs to
the metal center, serving as Lewis bases. Inthischapter,weshall focus primarilyon the chemical
behavior of the elements of the first transition series. (Rice University, 2015 : 1080)
Cl2(g) + 2KBr(aq) → 2KCl(aq) + Br2(aq)
Cl2(g) + 2KI(aq) →2KCl(aq) + I2(aq)
These reactions can be used as a test for bromide and iodide ions. Suppose an aqueous
solution of chlorine is added to a test tube containing either bromide or iodide ion. The
corresponding free halogen is formed in the water solution. It is readily identified by adding the
organic solvent methylene chloride, CH2Cl2, which dissolves the halogen, forming a colored layer
at the bottom of the test tube. Bromide ion gives an orange layer; iodide ion gives a violet layer.
Of course, neither bromine nor iodine is strong enough to oxidize chloride ion. Chlorine reacts
with water by being both oxidized and reduced.(Ebbing and Gammon, 2009)
All elements of fourth period transition have metal property. The property is resulted in all
transition elements have lower ionization energy, that is less than 1000 Kj/mol and its lower
electronegativity, that is less than 2.

Substance magnetic property is determined of its electron configuration. Diamagnetic


substance has does not have non pairs electron so that its electron spin is balanced. Paramagnetic
substance has a bit of non-pairs electron. The more having non-pairs electron, the stronger
attractive force by magnet pole. The elements of fourth period transitions created coloures
compounds, either in solid or in solution. The colour is related to the present of inclompete content
in sub-shell d. If sub-shell 3d is empty, the created compound is colourless. Compound from Sc3+,
and Ti4+. Compound from Zn2+ is also colourless due to have full content of sub-shell 3d.

The elements of fourth period transition have several oxidation levels. Oxidation level
diversity of fourth period elements is resulted in its valence electron occupies sub-shell 3d and 4s.
Energy level of those both sub-shell is closest so that fourth period elements can use electron in
sub-shell 3d and 4s for creating bond.

(Kasmadi, 2012)

C. Apparatus and Reagent


Apparatus Reagents
1. Test tube 0,25 M CuSO4 1 M KBr
2. Burner 1 M AgNO3 CHCl3
3. Erlenmeyer Iod Concentrated HCl
4. Pipe 1 M and 2 M NH3 Concentrated NH4Cl
5. Pieces of cloth Alcohol Chlorine
6. Colored flower Amilum Iron powder
7. Tunnel KBr crystal 1 M and 6 M H2SO4
8. Dropping pipet MnO2 Concentrated and 6 M
HNO3
CuSO4.5H2O 1 M K4Fe(CN)6

0,5 M FeSO4 6 m, 2 M, and 1 M


NaOH
1 M NaCl 0,1 M KMnO4
1 M KI Ethanol
D. Procedure
1. Preparation of halogen and its properties

Insert ½ teaspoon of Add 1 mL of


Cl into the tube. concentrated HCl
into graduated
cylinder

Immediately close the tube and Pour into the tube


connect the tube with the erlenmeyer
by the pipe

The formed chlorine gas will flow


into the water in the erlenmeyer

I Put a part of the Attach the


resulting chlorine coloured flower in
solution into the test the mouth of the
tube tube

Replace flowers with coloured Note the changes


pieces of cloth, wet and dry that occur
respectively.
Put 2 mL of Pour into a test
chlorine solution tube
into a graduated
cylinder

Add into that test tube Put 1 mL of


CHCl3into a
graduated cylinder

Shake the test Note the


tube CHCl3 layer

Put iodine into 2 Shake and note the


mL of water colour solution

Shake and Add 1 mL of CHCl3


note the
CHCl3 layer
Put 2 mL alcohol Pour into a test
into a graduated tube
cylinder

Note the color Dissolve a grain of


iodine in 2 mL of
alcohol

Take 2 mL of starch
solution into a
graduated cylinder

Mix 1 mL of
chlorine water Add dropwise
with 1 mL of KBr solution
CHCl3

Perform the
same
experiment with Shake the test
Note the colour
1 mL of KI tube
change occurs
solution
Enter iodine into
1 mL water Add CHCl3

Add 1 mL of Shake the test


NaCl solution tube

Put 2 mL of Pour into a test


NaCl solution tube
into a graduated
cylinder

Put 2 mL of KI
Pour into a test solution into a
tube graduated
cylinder

Put 2 mL of
KBr solution Pour into a test
into a graduated tube
cylinder

Take the
Add into each
deposits and Record the
tube a few drops
check using 1 M colour of the
of AgNO3
NH3 solution precipitate
solution to form
(dissolve or not)
precipitate
2. Complex Ion Formation

Put a few
CuSO4.5H2O Clip the test
crystals into tube and heat it
fireproof test horizontally
tube

Once the
Observe what Add a few drops substance
happened of water changes colour,
allow to cool the
test tube

Put each 1 mL In the first tube,


of 0,25 M add 2 M NH3
dropwise until
CuSO4 into 3
excess
pieces of tube

In the third tube, In the second


add concentrated tube, add 2 M
HCl dropwise NaOH dropwise
until the colour until excess
changes

Dilute with Add


Note the colour
water twice concentrated
change
NH4Cl
3. Typical Properties of Transition Elements
Iron

Put each 0,1 g of Put 5 mL of 1 M


iron powder into H2SO4 into a
2 pieces of tube graduated
cylinder

After the
reaction Pour into the
complete, add 5 first test tube
mL of water

Pour the Pour the


solution into the Note the colour solution into the
filter device of the filtrate filter device

Add 1 mL of 1
M K4Fe(CN)6 in Put each 1 mL filtrate into 2 test tubes A,
tube A B (called filtrate 1)

Add 1 mL of 1 Record any


M NaOH in tube changes that
D occur
In the second
After the
tube, add 5 mL
reaction
of water and 5 complete, pour Note the colour
mL of the solution into of the filtrate
concentrated the filter device
HNO3

Put each 1 mL
Add 1 mL of 1 Add 1 mL of 1 filtrate into 2
M NaOH in M K4Fe(CN)6 in test tubes A, B
tube D tube A (called filtrate
1)

Record any
changes that
occur

E. Observation Sheet
1. Preparation of halogen and its properties
No Experiment Observation
There are heat and yellow bubbles at long
1 Kaporit + concentrated HCl
time
a. Chlorine with colored flower The flower color to be fade
b. Chlorine with wet colored There are no change
2 cloth / fabric
c. Chlorine with dry colored There are no change
cloth / fabric
There are dome shaped layer under the tube
3 Chlorine with CHCl3
and concave layer at the up of tube
Yellow clear layers
a. Iodine in water
4
There are 2 layer, orange clear color in the up
b. Iodine in CHCl3
and purple under the tube
a. Iodine in alkohol Dark brown solution
5 b. Iod solution with amilum The color to be dark black
solution
+ CCl4 there are two layers
6 a. Chlorine water + CCl4 + KBr + KBr there are partition between two layers
at the long time
+ CCl4 there are two layers
7 Iodine water + CCl4 + KI + KBr there are partition between two layers
at the fast time
8 Experiment Colour of precipitate + NH3 (aq)
NaCl + AgNO3 White Not dissolved
KI + AgNO3 Yellowish Not dissolved
KBr + AgNO3 Yellowish white Not dissolved
2. Complex ion formation
No Experiment Observation
a. CuSO4.5H2O crystal heated The color at the first is bright blue to be fade
1 b. Cooled, add water To be bright blue solution

Dark blue solution


a. CuSO4 + NH3
Transparant solution, dark blue precipitation
b. CuSO4 + NaOH
Bright green solution
c. CuSO4 + HCl
The color to be fade
2 d. Dissolved
- Bright blue solution
e. Dissloved, add NH4Cl
- There are two layers, bright blue and
transparant also bright blue precipitation
- Transparant green solution

3. Typical properties of transition elements


Iron
Filtrate 1 Filtrate 2
Reagent Colour : transparant with black Colour : transparant with black
precipitation precipitation
K4Fe(CN)6 The colour is greenness dark The colour is blues dark green
blue
NaOH Clear dark green and there are Clear yellow and there are
precipitate precipitation

F. Discussion
1. Preparation of Halogen and its properties
In the first experiment , we reacting between Ca(OCl)2 with a concentrated HCl. The reaction
as the following :
Ca(ClO)2 + 4HCl CaCl2 + 2H2O + 2Cl2
In this reaction, we get the result, there are heat and yellow bubbles at long time. This reaction
produces gas Cl2 , it can be recognized that smells stimulating. This result is appropriate with the
theory.
In the second experiment, there are some point. The first point is reaction between chlor and
coloured flower. In this point, the result is the colour of the flower to be fade. It is because chlor
oxidize colour essence on the flower. This result is appropriate with the theory. Then the second
point is reaction between chlor and wet cloth. In this point, the result is there are no change on the
cloth. Properly, there are white spots on the wet cloth because there are H2 which oxidize colour
essence on the cloth. The third point is reaction between chlor and dry cloth. But also in this point,
the result is there are no change. Properly, the colour of the cloth is fade. This happens because the
Cl2 solution in water is used as a purifying agent which is actually more played by the oxidation
activity of the hypochlorite ion than the dichlorine molecule itself.
In the third experiment, we reacting chlor with CHCl3. In this experiment, there are dome
shaped layer under the tube and concave layer at the up of tube. The upper is chlor that not polar
enough, and the lower is CHCl3that more polar. The layer formed because there are difference
electronegativity. This result is appropriate with the theory.
In the fourth experiment, we do some point. The first point is reation between iodine with
water. In this point, we get the clear yellow solution. This result is appropriate with the theory.
The reaction Iodine in water as following: I2 + H2O  HI + HOI. In the second , we reacting
iodine with CHCl3. In this point, There are 2 layer, orange clear color in the up and purple under
the tube, where the upper is iodine that nonpolar and the lower is CHCl3that polar. This result is
appropriate with the theory.
In the fifth experiment, we do some point. The first point is reaction between iodine and
alcohol. In this point, we get dark black solution. This result is appropriate with the theory. In the
second point, we react iodine solution with starch solution. In this point, we get the color of
solution to be dark black. This result is appropriate with the theory. When iodine is in contact with
amylum, a characteristic color is generated by the I2 amylum complex. No chemical bond is
visible in this case, but the polymer molecule of amylum wraps itself around the iodine molecule.
It is because of this nature that makes amylum an indicator of iodine determination.
In the sixth experiment, we react chlor water + CHCl3 + KBr. The reactions that occur are KBr
+ H2Cl + CHCl3 → KCl + BrCH2 + HCl . In this experiment, we get the result, there are partition
between two layers at the long time. This result is appropriate with the theory. In the seventh
experiment, we react chlor water + CHCl3 + KI. The occur reaction is KI + H2Cl + CHCl3 → KCl
+ ICH2 + HCl . In this experiment, we get the result, there are partition between two layers at the
fast time. This result is appropriate with the theory.
In the eight experiment, we do some point. The first point is reaction between NaCl + AgNO3.
The reaction as the following :
NaCl + AgNO3 NaNO3 + AgCl
In this point, we get AgCl precipitate with white colour. And then, after mix with NH3 also form
the precipitate. The reaction is :
AgCl + 2NH3 [Ag(NH3)2]+ + Cl-
Then th second point is reaction between KI + AgNO3. The reaction as the following :
KI + AgNO3 KNO3 + AgI
In this point, we get AgI yellowish precipitate. And then, after mix with NH3 also form the
precipitate. The reaction is :
AgI + 2NH3 [Ag(NH3)2]+ + I-
The third point is reaction between KBr + AgNO3. The reaction as the following :
KBr + AgNO3 KNO3 + AgBr
In this point, we get AgBr yellowish white precipitate. And then, after mix with NH3 also form the
precipitate. The reaction is :
AgBr + 2NH3 [Ag(NH3)2]+ + Br-

2. Complex Ion Formation


In this point, the first experiment is heated the CuSO4.5H2O crystal. In this experiment, we
get the result, the color at the first is bright blue to be fade. The bright blue water is the result of
CuSO4. And then, after it cooled there are form the precipitate and the colour become same with
the first colour. We can reverse this reaction by adding water back to the white copper(II) sulfate.
CuSO4 + 5H2O → CuSO4.5H2O
Because this reaction is reversible, we can write both reactions in the same equation.
CuSO4.5H2O(s) ↔ CuSO4(s) + 5H2O

Then we react CuSO4 and NH3. The occur reaction is:

CuSO4(aq) + NH3(aq) → [Cu(NH3)4]SO4(aq)

In this point experiment, we get the colour dark blue solution. The second point is mix between
CuSO4 + NaOH. The reaction as the following :
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4
In this point, the result is CuSO4 is dissolved and then any dark blue precipitate. The third point is
reaction between CuSO4 + HCl. The reaction as the following :
CuSO4 + HCl CuCl2 + H2SO4
In this point, we get bright green solution. And then dissolve and adding NH4Cl make the colour
of the solution become more clear.

3. Typical Properties of Transition Elements


This experiment, there are 2 filtrate where both is transparant with black precipitation. When the
first filtrate is added by K4Fe(CN)6, it become dissolve and the colour change into greenness dark
blue. When it added by NaOH, it is not dissolve and the colour is green clear and there are
precipitation. And when the second filtrate is added by K4Fe(CN)6, the colour change into blues
dark green. When it added by NaOH, it is not dissolve and the colour is yellow clear and there are
precipitation. The reaction as the following:
Fe(s) + H2SO4(aq) FeSO4(aq) + H2(g)
The put the filtrate (FeSO4) to 2 different tube, there are :
 2FeSO4 + K4[Fe(CN)6]  3K2SO4 + Fe3[Fe(CN)6]2
Blue
 FeSO4 + 2NaOH  Na2SO4 + Fe(OH)2
Dark blue
We also react iron powder with HNO3. And the filtrate isdark grey. The reaction is :
Fe(s) + 2HNO3(aq) Fe(NO3)2(aq) + H2(g)
And then the reaction for the filtrate is:
 2Fe(NO3)2 + K4[Fe(CN)6]  4KNO3 + Fe[Fe(CN)6]
Dark green
 Fe(NO3)2 + NaOH  2NaNO3 + Fe(OH)2
Clear

G. Conclussion

1. Halogen elements can be formed by oxidation reaction and the reactivity of halogen elements
based on our team experimentsis Cl > Br > I.
The reaction occur in the first experiment as the following :
Ca(ClO)2 + 4HCl CaCl2 + 2H2O + 2Cl2
AgCl + 2NH3 [Ag(NH3)2]+ + Cl-
NaCl + AgNO3 NaNO3 + AgCl
KI + AgNO3 KNO3 + AgI
AgI + 2NH3 [Ag(NH3)2]+ + I-
KBr + AgNO3 KNO3 + AgBr
AgBr + 2NH3 [Ag(NH3)2]+ + Br-
2. Halide ion can be identification by reaction with AgNO3 . The reaction that occured is:
NaCl + AgNO3 NaNO3 + AgCl
KI + AgNO3 KNO3 + AgI
KBr + AgNO3 KNO3 + AgBr
3. Complex ion has characteristic color. The reaction that occur in this experiment is :
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4
CuSO4 + HCl CuCl2 + H2SO4
NH3 will form complex ions with Cu2+ ion.
Cu [Ar] 4s1 3d10
Cu2+ [Ar] 3d9
It is sometimes useful to think about the electron configuration of the Cu2+ ion in terms of
the entire set of valence-shell orbitals. In addition to the nine electrons in the 3d subshell, the
Cu2+ ion has an empty 4s orbital and a set of three empty 4p orbitals.
Cu2+ [Ar] 4s0 3d9 4p0
The empty 4s and 4p orbitals on the Cu2+ion are used to pick up pairs of nonbonding
electrons from four NH3 molecules to form a Cu(NH3)42+ ion.

H. References
Ebbing, Darrell D, Gammon Steven D. 2009. General Chemistry. U.S.A: Houghton Mifflin
Company

Rice University. 2015. Chemistry. Texas : OpenStax College

Supardi, kasmadi imam. 2012. Kimia dasar II. Semarang: Unnes Press

I. Appendix
1. Problems
a. Preparation of halogen and its properties
1) Write all the occured reactions
Answer :
The reactions for this experiment are :
1. Chlorine + concentrated HCl
Ca(OCl)2 + 4HCl  CaCl2 + 2Cl2 + 2H2O
2. Iodine in water
I2 + H2O  HI + HOI
3. a. Chlorine water + CHCl3 + KBr
𝐶𝐻𝐶𝑙3
Cl2 + 2KBr → 2KCl + Br2
b. Chlorine water + CHCl3 + KI
𝐶𝐻𝐶𝑙3
Cl2 + 2 KI → 2 KCl + I2
4. Iodine water + CHCl3 +NaCl
I2 + NaCl 
5. a. NaCl + AgNO3  NaNO3 + AgCl
AgCl(s) + NH3(aq)  [Ag(NH3)2]+ + Cl-
b. KI + AgNO3  KNO3 + AgI
AgI(s) + NH (aq)  [Ag(NH3)2]+ + I-

c. KBr + AgNO3  KNO3 + AgBr


AgBr(s) + NH3 (aq) 
2) Sort the reactivity of halogen elements based on your experiments
Answer :
Cl > Br > I

b. Complex ion formation


1) NH3 solution containing NH3, NH+ and OH-. Which one from complex ions with Cu2+ ion ?
give an explanation.
Answer :
NH3 because NH3 is donor of electron. The reaction is :
Cu2+ + 4NH3  [Cu(NH3)4]2+

2) HCl solution containing H+ and Cl- ions. Which ions form complexes with Cu+ ion ? Give an
explanation.
Answer :
Cl- , because liganol is an anion or a neutral molecule. Ligan Cl- is weakness than H2O. The
reaction is :
Cu2+ + 4Cl-  [Cu(Cl)42-]

3) Write down all the reactions in this experiment


Answer :
The reactions for this experiment are :
1. CuSO4.5H2O crystal heated
CuSO4(s) + 5H2O(aq) CuSO4.5H2O(s)
2. a. CuSO4 + 4NH3  Cu(NH3)4SO4
b. CuSO4 + NaOH  [Cu(OH)2SO4]4- + 4Na+
c. CuSO4 + HCl  [CuCl2SO4]4- + 4H+
d. CuSO4 + 2HCl  CuCl2 + H2SO4
e. H2SO4 + 2NH4Cl  (NH4)2SO4 + 2HCl

c. Typical properties of transition elements


1) Write the all the occured reaction in this experiment
Answer :
Iron powder + H2SO4 :
Fe(s) + H2SO4(aq)  FeSO4(aq) + H2(g)
Filtrate 1 :
 2FeSO4 + K4[Fe(CN)6]  3K2SO4 + Fe3[Fe(CN)6]2
 3FeSO4 + 2K3[Fe(CN)6]  3K2SO4 + Fe3[Fe(CN)6]2
 FeSO4 + 2NaOH  Na2SO4 + Fe(OH)2
Iron powder + HNO3 :
Fe(s) + 2HNO3(aq)  Fe(NO3)2(aq) + H2(g)
Filtrate 2 :
 2Fe(NO3)2 + K4[Fe(CN)6]  4KNO3 + Fe[Fe(CN)6]
 3Fe(NO3)2 + 2K3[Fe(CN)6]  6KNO3 + Fe3[Fe(CN)6]
 Fe(NO3)2 + NaOH  2NaNO3 + Fe(OH)2

2) Write the half reactions for all redox reactions that occur in this experiment.
Answer :
Oxidation : Mn2+ + 2 H2O  MnO2 + 2 e- + 4 H+ x3
Reduction : MnO4- + 3 e- + 4 H+  MnO2 + 2 H2O x2

Oxidation : 3 Mn2+ + 6 H2O  3 MnO2 + 6 e- + 12 H+


Reduction : 2 MnO4- + 6 e- + 8 H+  2 MnO2 + 4 H2O
3 Mn + 2 MnO4 + 2 H2O  5 MnO2 + 4 H+
2+