Aluminium and Its Compounds

Mutia Salsabila Syaifuddin

1813442011
ICP of Chemistry Education / IV
Yudhi Priyatmo, S. Pd. M. Pd
Suriati Eka Putri, S.Si., M.Si
 APPROVAL SHEET

Complete report of Inorganic Chemistry I Experiment, which entitle

“Aluminium and It Compounds” arranged by :
name : Mutia Salsabila Syaifuddin
ID : 1813442011
class/group : ICP of Chemistry Education / IV (Four)
it has been checked well by Assistant and Assistant Coordinator and acceptable.

Makassar, July 2020

Assistant Coordinator Assistant

A. Cici Kurnia Abidin, S. Si Yudhi Priyatmo, S, Pd, M.Pd

Known by
Responsibility Lecture

Suriati Eka Putri, S.Si., M.Si

ID. 1988030520122002
A. TITLE OF EXPERIMENT
Aluminium and Its Compounds

B. OBJECTIVE OF EXPERIMENT
To learn about the properties of aluminium metal and it compound

C. LITERATURE REVIEW
1. General Background
Aluminum is the commonest metallic element in the Earth’s crust, being a
constituent of almost all silicate minerals. Weathering leaves deposits of the very
insoluble aluminum minerals AlO(OH) and Al(OH)3, known together as bauxite,
which forms the principal source of the element. The metal is extracted by
electrolysis of fused cryolite Na3[AlF6]. Although reactive when clean, the metal
easily forms a very resistant oxide film, which allows widespread applications as
a lightweight construction material and in cooking and other
vessels (Cox. 2004).
Because aluminum is a metal with a high negative standard reduction
potential, it might be expected to be very reactive. This is indeed the case. Why,
then, can aluminum be used as an everyday metal rather than consigned to the
chemistry laboratory like sodium? The answer is found in its reaction with oxygen
gas. Any exposed surface of aluminum metal rapidly reacts with dioxygen to form
aluminum oxide, Al2O3. Aluminum also is exceptional as a conductor of
electricity, hence its major role in electric power lines and home wiring. The
major problem with using aluminum wiring occurs at the connections. If
aluminum is joined to an electrochemically dissimilar metal, such as copper, an
electrochemical cell will be established under damp conditions. This development
causes oxidation (corrosion) of the aluminum. For this reason, use of aluminum in
home wiring is now discouraged (Canham and Tina. 2010)
Aluminium is a white, ductile, and melleable metal, the powder is grey. It
meltsat 6590 C. Exposed to air, aluminium objects are oxidized on the surface, but
not oxide layer protects the object from further oxidation. Dilute hydrochloric acid
dissolves the metal readily, dissolution is sower in dilute sulphuric or nitric acid :
2Al + 6H+ 2Al+ + 3H2
The dissolution process can be speeded up by the addition of some mercury (II)
chloride to the mixture. Concentrated hydrochloric acid also dissolves aluminium:
2Al + 6 HCl 2Al3+ + 3H2 + 6Cl-
Magnesium forms the bivalent cation Mg2+. Its oxide, hydroxide, carbonate, and
phosphate are insoluble; the other salts are soluble. They taste bitter. Some of the
salts are hygroscopic (Svehla. 1979).
All aluminum halides can be made by direct reaction, but AlF3 is best
produced by reaction with anhydrous HF. It has a structure based on corner-
sharing AlF6 octahedra. Solid AlCl3 has a polymeric layer structure, but in the gas
phase or nonpolar solvents is molecular and dimeric bromine and iodide have the
molecular dimeric form in the solid state. Aluminum halides are strong Lewis
acids and AlCl3 is frequently used as an acid catalyst, for example, in organic
Friedel-Crafts reactions (Cox. 2004).
Like other powdered metals, aluminum powder will burn in a fl ame to
give a dust cloud of aluminum oxide:
4Al(s) +3O2(g) 2Al2O3(s)
and aluminum will burn very exothermically with halogens, such as dichlorine:
2Al(s) +3Cl2(g) 2AlCl3(s)
Aluminum, like beryllium, is an amphoteric metal, reacting with both acid and
base:
2Al(s) + 6H+(aq) 2Al3+(aq) +3H2(g)
2Al(s) + 2OH-(aq) 6H2O(l) + 2[Al(OH)4]-(aq)+3H2(g)
(Canham and Tina. 2010)
Reaction of aluminium (III) ions use ammonium solution white gelatinous
precipitate of aluminium hydroxide, slightly and soluble in excess of the reagent.
The solubility is decreased in it’s the presence of ammonium salts owing to the
common ion effect. A small proportion of the precipitate passes into solution as
that colloidat aluminium hydroxide. To ensure complete precipitation with
ammonium solution, the aluminium solution is added in slight and the mixture
boiled until the liquid has a slight odor of ammonia when freshly precipitated, it
dissolves readily and strong acid and bases, but after boiling becomes sparingly
soluble:
Al3+ + 3NH3+ 3H2O Al(OH)3 + 3NH4+
(Svehla. 1979).
Aluminum forms many mixed oxides of which the aluminosilicates are
major constituents of minerals. In these compounds aluminum sometimes replaces
a portion of the silicon present as corner-sharing SiO4 groups . The mixed oxide
mineral spinel MgAl2O4 gives its name to an important structure type. One-half of
the octahedral holes and one-eighth of the tetrahedral holes are filled in a cubic
close-packed array of oxide ions. In the normal spinel form adopted by MgAl2O4
the divalent Mg2+ ion is in tetrahedral sites and the trivalent Al3+ is octahedral.
(See Topic H4 for other examples.) In the defect spinel structure of γ-Al2O3 a
fraction of the cation sites are occupied at random. Organoaluminum compounds
are dimeric but the bonding is different from that of halides as the bridging methyl
groups in Al2(CH3)6 must be held by three-center two-electron bonds similar to
those in diborane. Organometallic compounds of Ga, In and Tl are less stable than
for Al and do not dimerize (Cox, 2004).
Magnesium is found in nature as one component in a number of mixed-
metal salts such as carnallite, KMgCl3.6H2O, and dolomite, CaMg(CO3)2. These
compounds are not simply mixtures of salts but are pure ionic crystals in which
the alternating sizes of the cations confer on the crystal lattice a greater stability
than that conferred by either cation alone. When ignited, magnesium metal burns
with a bright white light. The intensity of the light is so great that damage to the
retina can occur. The combustion of magnesium powder was used in early
photography as a source of illumination:
2Mg(s) + O2(g) 2MgO(s)
The hydroxide is then fi ltered off and mixed with hydrochloric acid. The
resulting neutralization reaction gives a solution of magnesium chloride:
Mg(OH)2(s) + 2HCl(aq) MgCl2(aq) + 2H2O(l)
(Canham and Tina. 2010).
2. Result of Review
The Al corrosion was related to the hydration of its oxide film with OH−
ions, which is reported by Deng. In this solution, it is possible that Cl− ions not
OH− ions attacked the oxide film and produced pitting, destroying the oxide film
on the surface of Al and Mg. Following the Mg─H2O reaction, the pH of the
solution increased from ~6 to ~10 due to the production of the scarcely
water‐soluble Mg(OH)2. On the other hand, the─H2O reaction caused a
decrease in pH to values ranging between 2 and 4 because of the hydrolysis of
AlCl3 and the complexation reaction of the Al3+ ions (Wang, et al. 2018).
The aluminum powders used for γ-alumina production were obtained
through aluminum cans high-energy milling using a ball mill producing aluminum
chloride (AlCl3)
2Al + 6HCl 2AlCl3 + 3H2
Reactant addition was slow (3.0 mL min-1), because the reaction occurs violently
and releases large amounts of heat and hydrogen. Aluminum chloride was then
converted into aluminum hydroxide by reaction with sodium hydroxide solution
AlCl3 + 3NaOH Al(OH)3 + 3NaCl
The gel obtained which was not white as aluminum hydroxide, but pink. Another
synthesis was performed replacing sodium hydroxide by ammonium hydroxide as
the precipitating agent and the color was like brown too.
AlCl3 + 3NH4OH Al(OH)3 + 3NH4Cl
NH4Cl NH3 + HCl
In order to compare the textural properties of the γ-alumina produced from
aluminum powders with those of an alumina prepared by a conventional
method (Adans, et al. 2016).
Aluminum is a composition formed from aluminum ions which are
produce salt Salt dual of aluminum is approved with sulfate ions forming a
Crystal known as alum. Products produced in the reaction one of them is H2 gas
with marked the appearance of bubbles gas. When aluminum reacts all then gas
bubbles H2 disappear. Warm up at this stage aims to speed up the
reaction (Sumanik, et al. 2019).
 Therefore, it is necessary to analyze the relationship between the
microstructure of Co and Ni and Mg─H2O/Al─H2O reaction. Combining the
results of the Al and Mg reactions in salt solutions, it can be concluded that the
cooperation of Co, Ni, and anions affected the Al and Mg corrosion and hydrogen
generation reactions (Wang, et al. 2018).

D. APPARATUS AND CHEMICAL

1. Apparatus
a. Test tube (12 pieces)
b. Test tube rack (2 piece)
c. Beaker glass 100 ml (1 piece)
d. Graduated cylinder (2 pieces)
e. Bunsen burner (1 piece)
f. Tripod (1 pieces)
g. Gauze (1 piece)
h. Spatula (2 piece)
i. Wood clamp (1 piece)
j. Funnel (1 piece)
k. Smooth cloth (2 pieces)
l. Rough cloth (1 piece)
2. Chemicals
a. Aluminium(III) chloride anhydrous and 0.1 M (AlCl3)
b. Aluminium(III) chloride anhydrous and 2 M (AlCl3)
c. Aluminium(III) oxide (Al2O3)
d. Magnesium oxide (MgO)
e. Dilute solution of hydrochloric acid (HCl)
f.Magnesium chloride anhydrous and 0.1 M (MgCl2)
g. Ammonium hydroxide solution 0.1 M (NH4OH)
h. Aquadest (H2O)
i. Sodium hydroxide solution 0.1 M (NaOH)
j. Sodium hydroxide solution 2 M (NaOH)
 k. Methyl violet
l. Universal indicator
m. Filter paper
n. Matches

E. WORK PROCEDURES
a. Properties of aluminum hydroxide

10
drops of Few drops of
NH4OH NH4OH over
2mL
aluminium again
salt 0.1 M

Observed Observed
the change

Few drops of
NaOH 0.1 M NaOH

2mL
aluminium
salt 0.1 M

The solution 1 2 1 2
divided two

1 2
Observed the result

2mL of aluminium 3mL of

salt 2M NaOH 2M 3 drops of
metiiviolet

Filter the Wash

precipitate with H2O
b. Comparing the acid-base properties of aluminum chloride with magnesium
chloride

1 spoon of 10 drops of
AlCl3 H2O 1 spoon of 10 drops
anhydrate MgCl2 of H2O
crystal anhydrate
crystal

Measure Observed
the pH Measured Observed
the pH

1 spoon of 10 drops of
AlCl3 H2O 1 spoon of 10 drops
anhydrate MgCl2 of H2O
crystal anhydrate
crystal

Measure Observed
the pH Measured Observed
the pH

c. Comparing the properties of acid-base Al2O3 and MgO

1 spoon
Al2O3 crystal 1 spoon
MgO crystal
3 mL 3 mL
H2O H2O

Shaked Measure Shaked Measured

d the pH the pH

3 mL HCl 3 mL HCl
0.1 M 0.1 M
1 Al2O spoon
3
Al2O 1 spoon
3 crystal
crystal
MgO crystal

Shaked Measured Shaked Measured

the pH the pH

3 mL 3mL
NaOH NaOH
0.1 M 0.1 M
1 spoon
Al2O3 crystal 1 spoon
MgO crystal

Shaked Measured Shaked Measured

the pH the pH
d. Comparing the properties base of aluminum ion and magnesium ion
2mL 2mL
Al2Cl3 MgCl2

20 drops of
20 drops of
NaOH 0.1M
NaOH 0.1M

Measured Observed
Measured Observed
the pH
the pH

F. OBSERVATION RESULT
1. Properties of Aluminum Hydroxide
No. Activity Result
1. AlCl3 0,1M + 3 ml NH4OH + shaked Turbid solution
Add AlCl3 0,1M again until 5 ml The solution is more turbid
2. AlCl3 0,1M + 3 ml NaO 0,1M + Turbid solution
shaked
The solution was divided two:
Tube 1: Add more NaOH again Colorless solution
Tube 2: Add 3 ml HCl Colorless solution
3. AlCl3 2M + 3 ml NaOH 2M + Form precipitate
shaked
Filter + washed using H2O Form purple prescipitate
Add 3 drops metil violet
2. Comparing the acid-base properties of Al2O3 and MgCl2
No. Activity Result
1. AlCl3 + heated (2 spoon) Melt and a little gas
2 spoon MgCl2 + heated Not melting and much gas
2. 1 spoon AlCl3 + 10 drops H2O Yellow solution, pH = 2
1 spoon MgCl2 + 10 drops H2O Turbid solution, pH = 6
3. Comparing the acid-base properties of Al2O3 and MgO
No. Activity Result
 1. Al2O3 + 3 ml H2O Colorless solution, form
precipitate, pH = 6
2. MgO + 3 ml H2O Turbid solution, form
precipitate
pH = 9
3. Al2O3 + 3 ml HCl 0,1M Colorless, form precipitation,
pH = 1
4. MgO + 3 ml HCl 0,1M Turbid, form precipitation,
pH = 6
5. Al2O3 + 3 ml NaOH 0,1M Colorless, form precipitation
pH = 12
6. MgO + 3 ml NaOH 0,1M Turbid, form precipitation
pH = 14
4. Comparing the base properties of Aluminum Ion and Magnesium Ion
No. Activity Result
1. Al2Cl3 check pH pH = 4
2. MgCl2 check pH pH = 6
3. Al2Cl3 + 20 drops NaOH 0,1M and Turbid, and pH = 5
check it’s pH
4. MgCl2 + 2 ml NaOH 0,1M and Turbid, and pH = 6
check it’s pH

G. DISCUSSION
Aluminium adalah logam yang putih, ulet, dan mudah dibentuk, bubuknya
berwarna abu-abu. Ini meltsat 6590 C. Terkena udara, benda-benda aluminium
teroksidasi di permukaan, tetapi tidak lapisan oksida melindungi objek dari
oksidasi lebih lanjut (Svehla. 1979). Aluminium adalah komposisi yang terbentuk
dari ion aluminium yang menghasilkan garam-garam ganda dari aluminium
disetujui dengan ion sulfat membentuk Kristal yang dikenal sebagai tawas.
Produk yang dihasilkan dalam reaksi salah satunya adalah gas H2 dengan ditandai
munculnya gelembung gas. Ketika aluminium bereaksi semua maka gelembung
gas H2 menghilang. Pemanasan pada tahap ini bertujuan untuk mempercepat
reaksi (Sumanik, et al. 2019).
1. Sifat aluminium hidroksida
Tujuan dari percobaan ini yaitu untuk mengetahui sifat aluminium
hidroksida (Al(OH)3). Mula-mula langkah yang dilakukan yaitu dengan
menambahkan amonia encer kedalam larutan garam aluminium dan diperoleh
larutan berwarna keruh. Kemudian ditambahkan lagi dengan NH4OH berlebih,
sehingga diperoleh larutan yang berwarna semakin keruh. Larutan yang keruh ini
karna berkurangnya kelarutan yang disebabkan adanya garam ammonium. Hal ini
tidak sesuai teori, karena amonium hidroksida berperan sebagai zat pengendap
dan warnanya juga seperti cokelat (Adans, et al. 2016). Adapun reaksi yang
terjadi:
AlCl3 + 3NH4OH Al(OH)3 + 3NH4Cl
Reaksi penambahan amonia encer secara berlebih:
Al(OH)3 + NH4OH [Al(OH)4]- + NH4+
Selanjutnya dilakukan penambahan NaOH pada aluminium klorida (AlCl3)
menghasilkan larutan berwarna keruh. Kemudian larutan tersebut dibagi menjadi
dua bagian. Pada bagian pertama direaksikan kembali dengan NaOH. Hasil yang
diperoleh yaitu larutan tidak berwarna. Hal ini tidak sesuai dengan teori bahwa
aluminium klorida kemudian diubah menjadi aluminium hidroksida melalui reaksi
dengan larutan natrium hidroksida menghasilkan gel yang tidak putih seperti
aluminium hidroksida, tetapi merah muda (Adans, et al. 2016).
Pada bagian kedua ditambahkan dengan dengan HCl, diperoleh latutan tidak
berwarna. Dari hasil percobaan ini dapat diketahui bahwa aluminium dapat larut
dalam larutan asam. Hal ini terjadi karena penambahan suatu asam (HCl) yang
berlebih menyebabkan hidroksida melarut. Hal tersebut menunjukkan bahwa
Al(OH)3 bersifat amfoter karena bereaksi dengan basa dan asam. Adapun
persamaan reaksinya:
AlCl3 + 3NaOH Al(OH)3 + 3NaCl
Al(OH)3 + NaOH Na[Al(OH)4]
Al(OH)3 + 3HCl AlCl3 + 3H2O
 Percobaan selanjutnya yaitu dengan mereaksikan AlCl3 dengan NaOH dan
diperoleh larutan yang terdapat endapan, yang merupakan endapan Al(OH)3.
Selanjutnya endapan yang terbentuk disaring untuk memisahkan endapan dengan
larutan. Kemudian endapan dicuci dengan air dingin. Hal ini berfungsi untuk
membersihkan endapan dari zat-zat pengotor. Perubahan warna dari putih menjadi
ungu maka endapan Al(OH)3 yang diperoleh bersifat basa. Perubahan endapan
menunjukkan bahwa endapan Al(OH)3 yang diperoleh bersifat basa. Hal ini
dikarenakan adanya efek ion sekutu, serta berkurangnya kelarutan karena adanya
garam-garam amonia. Adapun reaksi yang terjadi:
AlCl3 + 3NaOH Al(OH)3 + 3NaCl
2. Membandingkan aluminium klorida dan magnesium klorida.
Percobaan ini bertujuan untuk membandingkan sifat kelarutan dari AlCl3
dan MgCl3. Percobaan ini dilakukan dengan memansakan padatan AlCl3 dan
MgCl3 dalam tabung reaksi hingga diperoleh uap air pada dinding. Uap pada
dinding pada tabung disebabkan AlCl3 memiliki densitas yang besar. Pada
percobaan ini aluminium menghasilkan gas klor dan aluminium oksida. Adapun
reaksinya:
2AlCl3 + Cl2 Al2O3 + 3Cl2
Pemanasan pada serbuk MgCl2 tidak meleleh dan banyak menghasilkan gas, hal
ini sesuai dengan teori dimana serbuk AlCl3 dan MgCl2 , MgCl2 akan lebih cepat
meleleh dibandingkan serbuk AlCl3 karena AlCl3 memiliki titik leleh yang lebih
tinggi yakni 660oC sedangkan MgCl2 memiliki titik leleh 649oC, maka panas
yang dibutuhkan untuk mengatasi daya tarik diantara ion-ion kecil disebabkan
muatannya hanya +2 sedangkan pada serbuk AlCl3 muatannya +3 sehingga panas
yang dibutuhkan lebih besar.
. Perbedaan titik leleh pada kedua senyawa disebabkan karena perbedaan
jari-jari ionik magnesium yang lebih besar dari pada ion aluminium, sehingga
kerapatan aluminium leih besar dibandingkan dengan magnesium. Adapun reaksi
yaitu:
2AlCl3 + 3/2 O2 Al2O3 + 3Cl2
2MgCl2 + O2 2MgO + 2Cl2
 Percobaan kedua yaitu dengan melarutkan AlCl3 anhidrat dan MgCl2
anhidrat dengan aquades. Pada AlCl3, diperoleh AlCl3 yang larut dalam H2O dan
menimbulkan panas dengan larutan warna kuning pada larutan dengan pH larutan
yaitu 2 hal ini menandakan bahwa larutan bersifat asam pada AlCl3. Sedangkan
pada MgCl2 diperoleh MgCl2 berwarna keruh menimbulkan panas pada larutan
dengan pH yaitu 6. Hal ini menandakan larutan bersifat asam, namun AlCl3 lebih
bersifat asam. Hal tersebut mennjukkan bahwa AlCl3 dan MgCl2 berlangsung
reaksi eksoterm karena menghasilkan panas. Adapun reaksinya:
AlCl3 + 6H2O [Al(H2O)6]3+ + 3Cl-
MgCl2 + 6H2O [Mg(H2O)6]2+ + 2Cl-
Berdasarkan percobaan dapat diketahui bahwa aluminium dalam bentuk ion
kompleks memiliki tingkat keasaman yang lebih besar dibandingkan dengan
magnesium dalam bentuk kompleks.
3. Membandingkan sifat asam basa Al2O3 dan MgO
Percobaan ini bertujuan untuk membandingkan sifat asam basa Al2O3 dan
MgO. Langkah awal yang dilakukan yaitu Al2O3 dilarutkan dalam air dan
diperoleh larutan bening dan terdapat endapan pada larutan, pH larutan yaitu 6.
Hal ini menunjukkan bahwa Al2O3 tidak dapat larut dalam air. Hasil yang
diperoleh telah sesuai dengan teori bahwa Al2O3 akan membentuk lapisan nonpori
berupa endapan, yang dapat menyebabkan reaksi lebih lanjut tidak dapat terjadi.
Karena ion oksida dalam Al2O3 terlalu kuat dalam kisi padatannya untuk bereaksi
dengan air. Adapun reaksinya:
Al2O3 + H2O
Selanjutnya MgO dilarutkan dengan air menghasilkan larutan keruh dan ada
endapan, pH larutan yaitu 9. Hal ini menandakan bahwa MgO dapat larut dalam
H2O. Hal ini sesuai dengan teori bahwa MgO dapat larut dalam air meskipun agak
sulit (sukar). Adapun reaksinya:
MgO + H2O Mg(OH)2
Percobaan selanjutnya yaitu mereaksikan Al2O3 dengan HCl. Hasil yang
diperoleh yaitu larutan tidak larut, keruh, dan terdapat endapan dengan pH = 1.
Hal ini menunjukkan bahwa Al2O3 dapat bereaksi dengan HCl (asam). Adapun
reaksinya:
Al2O3 + 6HCl 2AlCl3 + 3H2O
Selnjutnya MgO dilarutkan dalam HCl menghasilkan larutan berwarna
keruh dan terdapat endapan, pH larutan yaitu 6. Hal ini menunjukkan bahwa MgO
dapat bereaksi dengan HCl membentuk MgCl2 dan pH pada suasana
basamenunjukkan bahwa MgO bersifat basa.Dalam percobaan ini telah sesuai
dengan teori yaitu MgO bereaksi dengan HCl encer untuk menghasilkan larutan
MgCl2 yang bersifat basa (Svehla, 1985). Adapun reaksinya:
MgO + 2HCl MgCl2 + H2O
Selanjutnya mereasikan Al2O3 dengan NaOH dan menghasilkan larutan
tidak larut, bening, dan terdapat endapan, pH larutan yaitu 12. Hasil yang
diperoleh menandakan bahwa reaksi Al2O3 dengan NaOH tidak larut. Hal ini
sesuai dengan teori bahwa Al2O3 dan NaOH tidak larut. Hal ini sesuai dengan
teori bahwa Al2O3 dan NaOH akan menghasilkan larutan natrium
tetrahidroksoaluminat yang mengendap. Adapun reaksinya:
Al2O3 + 2NaOH + 3H2O 2Na[Al(OH)4]
Sedangkan MgO direaksikan dengan NaOH menghaslkan larutan keruh dan
terdapat endapan, pH larutan yaitu 14. Hal ini menandakan bahwa MgO tidak
bereaksi dengan NaOH karena keduanya bersifat basa. Adapun reaksinya:
MgO + NaOH
Berdasarkan percobaan dapat diketahui bahwa Al2O3 bersifat amfoter dan
MgO bersifat basa lerut dalam suasana asam.
4. Membandingkan sifat basa ion aluminium dan ion magnesium.
Percobaan ini bertujuan untuk mengetahui sifat basa dari ion aluminium dan
ion magnesium. Langkah awal yang dilakukan yaitu dengan mengukur pH
larutan. Hasil yang diperoleh yaitu Al2O3 memiliki pH yaitu 4 dan MgCl2 yaitu 6.
Keasaman Al2O3 lebih kuat dibandingkan MgCl2 karena aluminium dan
magnesium pada sistem periodi unsur, aluminium berada pada golongan III A dan
magnesium golongan II A, diketahui bahwa dari kiri kekanan unsur akan semakin
kuat menarik elektron dan keasaman semakin kuat (bertambah). Selanjutnya
masing-masing larutan Al2O3 dan MgCl2 ditambahkan NaOH dan diukur pH-nya.
Hasil yang diperoleh larutan keruh larut dengan pH aluminium dan magnesium
berturut-turut yaitu 5 dan 6. Hasil yang diperoleh sesuai dengan teori, bahwa jika
larutan garam aluminium dan magnesium direaksikan dengan basa (NaOH) maka
keasaman garam aluminium lebih besar.Adapun persamaan reaksinya yaitu:
Al2O3 + 3NaOH Al(OH)3 + 3NaCl
MgCl2 + 2NaOH Mg(OH)2 + 2NaCl

I. CONCLUSIONS AND SUGGESTIONS

1. Conclusions
Based on the experiments that have been carried out, it can be concluded
that Al(OH)3 is amphoteric that is it can dissolve in an acidic or basic atmosphere.
Aluminum chloride (AlCl3) has a higher melting point compared to Magnesium
chloride MgCl2. Aluminum chloride has greater solubility compared to
magnesium chloride. Magnesium oxide and aluminum oxide have basic
properties. Al3+ ion is more acidic than Mg2+ ions.
5. Suggestion
It is recommended that the repeat practice repeat 2 times for each test in
order to obtain clear results.
 BIBLIOGRAPHY

Adans, Ysla França, André Rosa Martins, Rodrigo Estevam Coelho. 2016. A
Simple Way to Produce γ-Alumina From Aluminum Cans by Precipitation
Reactions. Materials Research. Vol. 19. No. 5.

Canham, Geoff Rayner and Tina Overton. 2010. Descriptive Inorganic Chemistry
Fifth Edition. New York : W. H. Freeman and Company.

Cox, P.A.2004. Instant Notes: Inorganic Chemistry. New York: BIOS Scientific.

Sumanik, Novike Bela, John Yoro Parlindungan, Rosalinda Zeniona Maarebia.

2019. Analisis Kandungan Aluminium Dalam Kaleng Bekas Untuk
Pembuatan Tawas, Musamus Journal of Science Education. Vol 2. No . 1
Print ISSN: 2622-7851, Online e-ISSN: 2622-786x.

Svehla. G. 1979. Vogel's Qualitative Inorganic Analysis Seventh Edition.

Longman : England.

Wang, Xiuman, Qian Zhang, Xiaofeng Shi, et al. 2018. Synergistic Effect of The
Fresh Co, Ni, and Anion Ions on Aluminum or Magnesium with Water
Reactions. International Journal of Energy Research. Vol. 43.
Scanned with CamScanner
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 DOCUMENTATION

1. Properties of Aluminium Hydroxide

AlCl3 0,1 M + 3 ml NH4OH Add AlCl3 0,1 M again until

+ Shaked 5 mL

AlCl3 0,1 M + 3 ml NaOH Tube 1 : Add more NaOH

0,1 M + Shaked again

Tube 2 : Add 3ml HCl

 AlCl3 2 M + 3 ml NaOH 2 Filter
M+ Shaked AlCl3 2 M + 3

Add 3 drops metil violet

2. Comparing the acid-base properties of AlCl3 and MgCl2.

AlCl3 and MgCl2 2 spoons Heated

AlCl3 and MgCl2 1 spoon 10 drops aquadest

Check pH
3. Comparing the acid-base properties of Al2O3 and MgO.

Al2O3 and MgO 1 spoon 3 mL aquadest

MgO + 3 ml H2O MgO + 3 ml H2O

Check pH
MgO + 3 ml H2O

Al2O3 and MgO 1 spoon 3 ml HCl 0,1 M

MgO + 3 ml H2O MgO + 3 ml H2O

Al2O3 and MgO 1 spoon 3 ml NaOH 0,1 M

MgO + 3 ml H2O MgO + 3 ml H2O
 Check pH
MgO + 3 ml H O
4. Comparing the base properties of Aluminum2 ion and Magnesium ion

Check pH Al2Cl3 and 2 ml NaOH 0,1 M to Al2Cl3

MgCl2 and MgCl2
MgO + 3 ml H2O MgO + 3 ml H2O

Check pH
MgO + 3 ml H2O
Materials Research. 2016; 19(5): 977-982 © 2016
DOI: http://dx.doi.org/10.1590/1980-5373-MR-2016-0310

A Simple Way to Produce γ-Alumina From Aluminum Cans by Precipitation Reactions

Ysla França Adansa, André Rosa Martinsa, Rodrigo Estevam Coelhob, Cesário Francisco das Virgensc,

Adriana Daniela Ballarinid, Luciene Santos Carvalhoa*

a
Grupo de Pesquisa em Materiais e Catálise, Instituto Federal da Bahia, Campus Camaçari,
Loteamento Espaço Alpha, s/n, BA 522, Limoeiro, 42.802-590, Camaçari, BA, Brazil
b
Grupo de Pesquisa em Processamento e Caracterização de Materiais, Instituto Federal da Bahia, Rua
Emídio dos Santos, s/n, Barbalho, 40.301-015, Salvador, BA, Brazil
c
Grupo de Estudos em Materiais e Catálise, Universidade do Estado da Bahia – UNEB, Rua Silveira
Martins, 2555, Cabula, 41.150-000, Salvador, BA, Brazil
d
Instituto de Investigaciones en Catálisis y Petroquímica “Ing. José Miguel Parera” – INCAPE,
Facultad de Ingeniería Química – FIQ, Universidad Nacional del Litoral – UNL, Colectora Ruta
Nacional No 168, Km 0, Paraje El Pozo, 3000, Santa Fe, Argentina

Received: April 18, 2016; Revised: June 18, 2016; Accepted: June 25, 2016

In this paper, a new way for γ-alumina synthesis was proposed, the raw material being aluminum
powders obtained by high-energy milling of aluminum cans. This seems a good option for this
metal recycling and energy saving, as well as hydrogen production. The materials were prepared
by precipitation techniques, in which aluminum powders reacted with hydrochloric acid, giving
aluminum chloride, which was subsequently transformed into aluminum hydroxide by reaction
with ammonium hydroxide or sodium hydroxide as precipitant agents, and finally into γ-alumina by
calcination. Results showed that the used preparation methods gave a γ-alumina structure, confirmed
by XRD, with surface areas values (174 and 204 m2 g-1) close to those of a commercial γ-alumina
Cyanamid Ketjen (180 m2 g-1) or an alumina prepared by a typical precipitation route (203 m2 g-1).
Using sodium hydroxide as precipitant agent turned out to be more ecologically compatible since
it did not release harmful environmental compounds.

Keywords: Precipitation, γ-Alumina, Aluminum Cans, High-energy Milling, Recycling

1. Introduction of alumina and all of them use aluminum scraps and sulfuric
acid or mercury compounds in the reactions.
γ-Alumina is widely employed as a catalyst or catalyst
The aim of this study was to develop a different route
support in several chemical processes, such as ammonia
for γ-alumina synthesis, from using aluminum powders
synthesis, synthesis gas and hydrogen production, oils
obtained by high-energy milling of aluminum cans as
hydrogenation, petroleum refining, automotive emissions
starting material. Using powders instead of aluminum
control, among others1,2. Some characteristics that make it
scraps is interesting because increases the contact surface
attractive for these applications are its high surface area,
and hence the rate of chemical reactions and it is not
high thermal and chemical stability and high mechanical
necessary sulfuric acid to digest the sample. According
strength2,3. However, alumina is mainly produced by Bayer
to the proposed method, two subsequent precipitation
process4, a high-energy consumption technology. On the other
reactions were carried out: first aluminum with hydrochloric
hand, alumina can be obtained by precipitation methods5,
acid and then the aluminum chloride formed with sodium
by sol-gel methods6, or even from kaolin7,8.
hydroxide or ammonium hydroxide as precipitating agents
It is known that the aluminum cans recycling saves up to
of aluminum hydroxide gel. Other acids such as nitric
95 % energy. By recycling 1 kg aluminum cans, for instance,
or sulfuric ones could also have been used to obtain an
one can save 8 kg bauxite, 4 kg chemical products and 14
intermediate aluminum salt such as aluminum nitrate or
kWh power can be saved9. Recycling of aluminum is then of
aluminum sulfate, respectively. However, sulfur oxides
great interest from economic, energetic and environmental
(SOx) or nitrogen oxides (NOx) could be formed as by-
perspectives. In this line, with goal to contribute with new
products, which would cause environmental damage if
routes of this metal recycling, researchers10-13 proposed the
released for atmosphere.
conversion of aluminum scrap from beverage cans. These
Structure and morphology of the materials were investigated
methods involve expensive reactants or complexes reactions
by XRD, SEM, BET surface area and pore properties,
or releasing of harmful compounds to the environment, as
and were compared with those of an alumina prepared by
SO3. The majority employs sol-gel process in the synthesis
aluminum hydroxide precipitation from aluminum nitrate
and ammonium hydroxide.

* e-mail: prof.lucarvalho@gmail.com
978 Adans et al.
2. Materials and Methods
2.1 Obtaining aluminum powders
The aluminum powders used for γ-alumina production were
obtained through aluminum cans high-energy milling using a ball
mill. The ink was removed from the cans using varnish solvent
and then the cans were cut into 5 mm squares. The material was
processed in a horizontal attritor mill, designed and assembled by
Coelho14. Milling was performed at 1000 rpm for 1 h.
2.2. Preparation of γ-alumina from aluminum
powders
2.2.1. Al reaction with HCl and subsequently with
NaOH
According to this method, 4 g aluminum powder were
weighted in a beaker and after addition of water (100 mL)
reacted with hydrochloric acid solution (6 mol L -1,
100 mL), drop-to-drop, under constant stirring, producing
aluminum chloride (AlCl3), as described by Eq. 1.
2Al + 6HCl 2AlCl3 + 3H2 (1)
Reactant addition was slow (3.0 mL min-1), because
the reaction occurs violently and releases large amounts of
heat and hydrogen. Considering the stoichiometry of this
reaction from 100 g of aluminum are produced 125 L of
hydrogen, that if collected and stored, it can be used as fuel.
This is the goal of several studies15,16. However, the aim of
this work it was not hydrogen storage. Then, due to the high
inflammability of the produced hydrogen, it was released
to the atmosphere taking adequate safety measures during
the experiments.
Aluminum chloride was then converted into aluminum
hydroxide by reaction with sodium hydroxide solution (6
mol L-1), added drop-to-drop (8.0 mL min-1) and under
stirring, at room temperature. Eq. 2 represents this reaction.
AlCl3 + 3NaOH Al ]OH g3 + 3NaCl (2)
After maturation under constant stirring by 24 h, the
mixture was separated by centrifugation and the solid was
washed with ammonium hydroxide solution (1 %). The
gel obtained which was not white as aluminum hydroxide,
but pink, was dried (110 oC, 24 h), triturated in agate,
sieved (100-200 mesh) and calcined at 800 oC for 4 h.
According to the thermal transformation sequence of the
aluminum hydroxides17, the γ-alumina formation with
high surface area, takes place by heating the boehmite
precursor (AlOOH) between 450-750 oC. However,
in this work, the chosen calcination temperature was
800 oC, considering that most of catalytic processes,
which employ alumina as catalyst or support, operate
at high temperatures in the range of 600-900 oC. This
is the case, for example, of methane steam reforming
reactions to produce hydrogen and syngas18. The goal was
to assure the formation and preservation of γ-alumina
phase in the reaction temperatures.
Materials Research
The prepared sample was named LS1000-1. By this
method were obtained 10 g of dried sample and 6 g of calcined
sample (alumina). The calcined sample was like brown.
2.2.2. Al reaction with HCl and subsequently with
NH4OH
Another synthesis was performed replacing sodium
hydroxide by ammonium hydroxide as the precipitating
agent. The preparation procedure was the same described
above and the reaction between aluminum chloride and
ammonium hydroxide occurred as shown in Eq. 3. The
use of ammonium hydroxide as the precipitating agent is
interesting because during the calcination step (800 oC, 4 h)
ammonia (NH3) and hydrochloric gas (HCl) are eliminated
by ammonium chloride decomposition (Eq. 4), and thus do
not contaminate the final solid. However, the released gases
are harmful to health and the environment. The obtained
sample was named LA1000-1. The yield after drying and
calcination was similar to that obtained with LS1000-1
sample, and the color was like brown too.
AlCl3 + 3NH4 OH Al ]OH g3 + 3NH4 Cl (3)
NH4 Cl NH3 + HCl (4)
2.3. Preparation of γ-alumina by conventional
method
In order to compare the textural properties of the γ-alumina
produced from aluminum powders with those of an alumina
prepared by a conventional method, the material was also
obtained by simultaneous addition of 250 mL aluminum
nitrate solution (1.0 mol L -1) and 200 mL concentrated
ammonium hydroxide (30-32 %) into a beaker containing
water (100 mL) under constant stirring and pH 9-10. After
reactant addition, the system was kept under stirring for
24 h. Then, the white material was centrifuged and washed
with ammonium hydroxide, and the gel obtained was dried
(110 oC, 24 h), triturated in agate, sieved (100-200 mesh) and
calcined at 800 oC for 4 h. The yield was similar to that of
the samples prepared by the proposed methods. This sample
was identified as CA. Calcined solid was white.
2.4. Characterization of the solids obtained by
different methods
The thermal behavior of non-calcined materials was
evaluated by thermogravimetric analysis (TGA), heating
the sample from 22 to 950 oC, under N2 atmosphere. A TGA
51-H Shimadzu equipment was used.
Scanning Electron Microscopy (SEM) images of calcined
samples were obtained through VEGA 3 Tesca equipment
at 15 kV. Energy Dispersive X-Ray Spectroscopy (EDS)
analysis to identify the chemical qualitative composition
was performed in an X-act Oxford Instruments apparatus
coupled to the electron microscope.
Samples crystalline phases were identified by X-ray
diffraction (XRD). During the experiments performed in
Descriptive
Inorganic Chemistry
FIFTH EDITION

Geoff Rayner-Canham
Sir Wilfred Grenfell College
Memorial University

Tina Overton
University of Hull

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276 CHAPTER 12 • The Group 2 Elements: The Alkaline Earth Metals

The chemistry of beryllium is significantly different from that of the other

Group 2 elements because covalent bonding predominates in its compounds.
2! The very small beryllium cation has such a high charge density (1100 C?mm23)
H2
O that it polarizes any approaching anion, and overlaps of electron density occur.
Hence, the simple ionic compounds of beryllium tend to be found as tetra-
Be hydrates, such as BeCl2?4H2O, which actually consist of [Be(OH2)4]21?2Cl2 ions
H2O OH 2
in the crystal lattice. This tetraaquaberyllium ion, [Be(OH2)4]21, in which the four
OH 2
oxygen atoms of the water molecules are covalently bonded to the beryllium
FIGURE 12.2 Tetrahedral shape ion, is also the predominant species in aqueous solution. Four coordination is the
1
of the [Be(OH2)4]2 ion. norm for beryllium, because of the small size of the beryllium ion (Figure 12.2).
Although beryllium is definitely metallic, it has one property that is more
characteristic of nonmetals—an ability to form oxyanion species. “Normal”
metal oxides generally react with acids to give cations but not with bases to
form oxyanions. Thus, beryllium oxide is amphoteric (see Chapter 7, Section 7.5,
and Chapter 9, Section 9.4), reacting not only with hydronium ion to form the
tetraaquaberyllium ion, [Be(OH2)4]21, but also with hydroxide ion to form the
tetrahydroxoberyllate ion, [Be(OH)4]22:
BeO1s2 1 2 H3O1 1aq2 1 H2O1l2 S 3Be1OH2 2 4 4 21 1aq2
BeO1s2 1 2 OH2 1aq2 1 H2O1l2 S 3Be1OH2 4 4 22 1aq2
Beryllium and the other metals that exhibit amphoteric behavior (includ-
ing aluminum and zinc) are sometimes called “weak” metals because they tend
to be located close to the semimetals and to the semimetal/nonmetal boundary.
In the case of beryllium, it is actually located next to boron, on the semimetal/
nonmetal boundary. It is only because we fit the transition metal groups farther
down into the short form of the periodic table that there appears to be a gap
between beryllium and boron.

12.4 Magnesium

Magnesium is found in nature as one component in a number of mixed-metal

salts such as carnallite, KMgCl3?6H2O, and dolomite, CaMg(CO3)2. These com-
pounds are not simply mixtures of salts but are pure ionic crystals in which the
alternating sizes of the cations confer on the crystal lattice a greater stability than
that conferred by either cation alone. Thus, carnallite contains arrays of chloride
anions with interspersed potassium and magnesium cations and water molecules
in a ratio of 3:1:1:6. Another magnesium-containing mineral is magnesium sulfate
heptahydrate, MgSO4?7H2O, commonly called Epsom salts.

Reactions of Magnesium
When ignited, magnesium metal burns with a bright white light. The intensity
of the light is so great that damage to the retina can occur. The combustion of
magnesium powder was used in early photography as a source of illumination:
2 Mg1s2 1 O2 1g2 S 2 MgO1s2
 12.4 Magnesium 277

The combustion reaction is so vigorous that it cannot be extinguished by

using a conventional fire extinguisher material such as carbon dioxide. Burn-
ing magnesium even reacts with carbon dioxide to give magnesium oxide and
carbon:
2 Mg1s2 1 CO2 1g2 S 2 MgO1s2 1 C1s2
To extinguish reactive metal fires, such as those of magnesium, a class D fire
extinguisher must be used. (Classes A, B, and C are used to fight conventional
fires.) Class D fire extinguishers contain either graphite or sodium chloride.
Graphite produces a solid coating of metal carbide over the combusting sur-
face and effectively smothers the reaction. Sodium chloride melts at the tem-
perature of the burning magnesium and forms an inert liquid layer over the
metal surface; it too prevents oxygen from reaching the metal.
The chemistry of magnesium differs from that of the lower Group 2 metals.
Of particular importance, magnesium readily forms compounds containing
covalent bonds. This behavior can be explained in terms of its comparatively
high charge density (120 C?mm23; calcium’s charge density is 52 C?mm23).
For example, magnesium metal reacts with organic compounds called halo-
carbons (or alkyl halides) such as bromoethane, C2H5Br, in a solvent such as
ethoxyethane, (C2H5)2O, commonly called ether. The magnesium atom inserts
itself between the carbon and halogen atoms, forming covalent bonds to its
neighbors:
C2H5Br1ether2 1 Mg1s2 S C2H5MgBr1ether2
These organomagnesium compounds are referred to as Grignard reagents,
and they are used extensively as intermediates in synthetic organic chemistry.
We discuss Grignard reagents in more detail in Chapter 23, Section 23.4.

The Industrial Extraction of Magnesium

Magnesium is the third most common ion in seawater (after sodium and
chloride), and seawater is a major industrial source of this metal. In fact,
1 km3 of seawater contains about 1 million tonnes of magnesium ion. With
108 km3 of seawater on this planet, there is more than enough magnesium for
our needs.
The Dow Chemical extraction process is based on the fact that magnesium
hydroxide has a lower solubility than calcium hydroxide does. Thus, a suspen-
sion of finely powdered calcium hydroxide is added to the seawater, causing
magnesium hydroxide to form:
Ca1OH2 2 1s2 1 Mg21 1aq2 S Ca21 1aq2 1 Mg1OH2 2 1s2
The hydroxide is then filtered off and mixed with hydrochloric acid. The resulting
neutralization reaction gives a solution of magnesium chloride:
Mg1OH2 2 1s2 1 2 HCl1aq2 S MgCl2 1aq2 1 2 H2O1l2
The solution is evaporated to dryness, and the residue is placed in an elec-
trolytic cell similar to the Downs cell used for the production of sodium.
The magnesium collects on the surface of the cathode compartment and is
 13.6 Aluminum 301

typical. Ionic chlorides are solids that dissolve in water to form hydrated cations
and anions. However, the typical small-molecule covalent chloride is a gas or
liquid at room temperature and reacts violently with water. For example, bub-
bling boron trichloride (a gas above 128C) into water produces boric acid and
hydrochloric acid:
BCl3 1g2 1 3 H2O1l2 S H3BO3 1aq2 1 3 HCl1aq2
We can predict the products of these reactions in terms of the relative elec-
tronegativities of the two atoms. In this case, the electronegativity of chlorine
is much greater than that of boron. Hence, as a water molecule approaches
the boron trichloride molecule, we can picture the partially positive hydro-
gen being attracted to the partially negative chlorine atom, while the partially
negative oxygen atom is attracted to the partially positive boron atom (Figure
13.15). A bond shift occurs, and one chlorine atom is replaced by a hydroxyl
group. When this process happens two more times, the result is boric acid.

(% FIGURE 13.15 First step of

(% Cl (%
the postulated mechanism for
Cl Cl
(! (% (% (! (% (! (! (% hydrolysis of boron trichloride.
B Cl Cl B O H B O
(% (% (!
Cl (% (! Cl H
Cl H (% (!
Cl H

13.6 Aluminum

Because aluminum is a metal with a high negative standard reduction poten-

tial, it might be expected to be very reactive. This is indeed the case. Why, then,
can aluminum be used as an everyday metal rather than consigned to the
chemistry laboratory like sodium? The answer is found in its reaction with Al Al Al Al Al
oxygen gas. Any exposed surface of aluminum metal rapidly reacts with
Al Al Al Al Al
dioxygen to form aluminum oxide, Al2O3. An impermeable oxide layer,
between 1024 and 1026 mm thick, then protects the layers of aluminum
Al Al Al Al Al
atoms underneath. This can happen because the oxide ion has an ionic radius
(124 pm) similar to the metallic radius of the aluminum atom (143 pm). As a
result, the surface packing is almost unchanged because the small aluminum O O
ions (68 pm) fit into interstices in the oxide surface structure. The process is
shown in Figure 13.16.
_ _ _ _ _
To increase their corrosion resistance, aluminum products are anodized. O2 O2 O2 O2 O2
In other words, the aluminum product is used as the anode in an electro- Al3+
chemical cell, and additional aluminum oxide is deposited as an electrolytic Al Al Al Al Al
product over the naturally formed layers. This anodized aluminum possesses
Al Al Al Al Al
an oxide layer about 0.01 mm thick, and this very thick oxide coating has the
useful property of absorbing dyes and pigments so that a colored surface FIGURE 13.16 Formation of a
can be produced. single oxide layer on the surface
The particular attraction of aluminum as a construction metal is its low of aluminum metal. The small
density (2.7 g?cm23), second only to that of magnesium (1.7 g?cm23)—disregarding aluminum 31 ions are indicated
the very reactive alkali metals. For instance, compare the density of aluminum by the solid circles.
302 CHAPTER 13 • The Group 13 Elements

with that of either iron (7.9 g?cm23) or gold (19.3 g?cm23). Aluminum is a
good conductor of heat, a property accounting for its role in cookware. It is
not as good as copper, however. To spread heat more evenly from the electri-
cal element (or gas flame), higher-priced pans have a copper-coated bottom.
Aluminum also is exceptional as a conductor of electricity, hence its major role
in electric power lines and home wiring. The major problem with using aluminum
wiring occurs at the connections. If aluminum is joined to an electrochemically
dissimilar metal, such as copper, an electrochemical cell will be established under
damp conditions. This development causes oxidation (corrosion) of the aluminum.
For this reason, use of aluminum in home wiring is now discouraged.

Chemical Properties of Aluminum

Like other powdered metals, aluminum powder will burn in a flame to give a
dust cloud of aluminum oxide:
4 Al1s2 1 3 O2 1g2 S 2 Al2O3 1s2
and aluminum will burn very exothermically with halogens, such as dichlorine:
2 Al1s2 1 3 Cl2 1g2 S 2 AlCl3 1s2
Aluminum, like beryllium, is an amphoteric metal, reacting with both acid and
base:
2 Al1s2 1 6 H1 1aq2 S 2 Al31 1aq2 1 3 H2 1g2
2 Al1s2 1 2 OH2 1aq2 1 6 H2O1l2 S 2 3Al1OH2 4 4 2 1aq2 1 3 H2 1g2
In aqueous solution, the aluminum ion is present as the hexaaquaaluminum
ion, [Al(OH2)6]31, but it undergoes a hydrolysis reaction to give a solution of
the pentaaquahydroxoaluminum ion, [Al(OH2)5(OH)]21, and the hydronium
ion, and then to the tetraaquadihydroxoaluminum ion:
3Al1OH2 2 6431 1aq2 1 H2O1l2 ∆ 3Al1OH2 2 5 1OH2421 1aq2 1 H3O1 1aq2
3Al1OH2 2 5 1OH2 4 21 1aq2 1 H2O1l2 ∆ 3Al1OH2 2 4 1OH2 2 4 1 1aq2 1 H3O1 1aq2
Thus, solutions of aluminum salts are acidic, with almost the same acid ioniza-
tion constant as ethanoic (acetic) acid. The mixture in antiperspirants com-
monly called aluminum chlorhydrate is, in fact, a mixture of the chloride salts
of these two hydroxo ions. It is the aluminum ion in these compounds that acts
to constrict pores on the surface of the skin.
Addition of hydroxide ion to aluminum ion first gives a gelatinous precipitate
of aluminum hydroxide, but this product redissolves in excess hydroxide ion to
give the aluminate ion (more precisely called the tetrahydroxoaluminate ion):
OH2 OH2
3Al1OH2 2 6431 1aq2 ¡ Al1OH2 3 1s2 ¡ 3Al1OH2 44 2 1aq2
As a result, aluminum 31 is soluble at low and high pH’s but insoluble under
neutral conditions (Figure 13.17). Aluminum hydroxide is used in a number of
antacid formulations. Like other antacids, the compound is an insoluble base
that will neutralize excess stomach acid:
Al1OH2 3 1s2 1 3 H1 1aq2 S Al31 1aq2 1 3 H2O1l2
 Instant Notes

Inorganic Chemistry
Second Edition

P.A.Cox
Inorganic Chemistry Laboratory,
New College, Oxford, UK

LONDON AND NEW YORK

 © Garland Science/BIOS Scientific Publishers, 2004
First published 2000
Second edition 2004
All rights reserved. No part of this book may be reproduced or transmitted, in any form or by any means, without permission.
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 Section G—Chemistry of non-transition metals
G5
GROUP 13: ALUMINUM TO THALLIUM

Key Notes
The elements Aluminum is the commonest metallic element on Earth, occurring
widely in aluminosilicate minerals and in deposits of the hydroxide
bauxite. It is very electropositive and potentially very reactive, but
forms a stable oxide film. Gallium, indium and thallium are rarer and
less electropositive.
MIII aqueous chemistry Al3+ is amphoteric and complexes strongly with hard ligands. Ga3+ and
In3+ are similar, but Tl3+ is a strong oxidizing agent and shows soft
complexing properties.
MIII compounds AlIII is octahedral in fluorides and in most oxides (including many
complex oxides), and tetrahedral with larger or less electronegative
atoms (and sometimes also in oxides). Heavier halides form molecular
dimers Al2X6. The tetrahedral [AlH4]− complex and dimeric alkyls are
also formed. The heavier elements of the group form less stable
compounds, especially TlIII.
Lower oxidation states Stability of MI increases down the group. Tl+ is strongly basic and
shows some resemblance to group 1 cations in its solution and solid-
state chemistry. Mixed valence and metal-metal bonded compounds of
Ga, In and Tl are also known.
Related topic Introduction to non-transition metals (G1)

The elements
The elements aluminum, gallium, indium and thallium have valence electron configurations (ns)2(np)1 and for the lighter
elements their chemistry is dominated by the +3 oxidation state. The group trends are very different, however, from
those in groups 1 and 2. The Al3+ ion has a large charge/radius ratio and is strongly polarizing, so that significant
deviations from simple ionic behavior are often observed. The filling of the d shells (and 4f in period 6) leads to
decreased electropositive character for Ga, In and Tl similar to that shown in group 12 (see Topics G1 and G4). There
is also a progressive stabilization of lower oxidation states down the group.
Aluminum is the commonest metallic element in the Earth’s crust, being a constituent of almost all silicate minerals
(see Topic J2). Weathering leaves deposits of the very insoluble aluminum minerals AlO(OH) and Al(OH)3, known
together as bauxite, which forms the principal source of the element. The metal is extracted by electrolysis of fused
cryolite Na3[AlF6]. Although reactive when clean, the metal easily forms a very resistant oxide film, which allows
widespread applications as a lightweight construction material and in cooking and other vessels.
202 SECTION G—CHEMISTRY OF NON-TRANSITION METALS

Fig. 1. Frost diagram showing the oxidation states of Al, Ga, In, Tl in aqueous solution at pH=0.

Ga, In and Tl are much less common elements, obtained in small amounts from sulfide minerals of other elements
and used only in specialized applications. The metals are less reactive than aluminum; Fig. 1 shows a Frost diagram in
which the much larger negative slope (negative electrode potential; see Topic E5) of Al is apparent. Thallium
compounds are extremely toxic but do not normally pose an environmental hazard because they are little used.

MIII aqueous chemistry

Al3+ is amphoteric and will dissolve in acidic and alkaline solutions (see Topic E2). The [Al(H2O)6]3+ ion is formed at
low pH but undergoes increasing protolysis as the pH increases above four, and polymeric species such as [Al13O4(OH)
7+
24(H2O)12] can be identified. The very insoluble Al(OH)3 is formed at neutral pH but redissolves above pH 10:

Al3+ shows typically ‘hard’ complexing behavior and has a particularly strong affinity for negative charged and/or
chelating ligands, such as oxalate and EDTA (see Topic E3).
Ga3+ is similar to Al3+ but In3+ is more basic. Tl3+ differs as it is a strong oxidizing agent, readily forming Tl+ (see below
and Fig. 1). It also shows strong class b or ‘soft’ complexing behavior, although not so marked as that of Hg2+ (see
Topic G4).

MIII compounds
All aluminum halides can be made by direct reaction, but AlF3 is best produced by reaction with anhydrous HF. It
has a structure based on corner-sharing AlF6 octahedra (similar to ReO3; see Topic D3). Solid AlCl3 has a polymeric
layer structure, but in the gas phase or nonpolar solvents is molecular and dimeric Al2Cl6 (see Topic C9, Structure 1).
The bromine and iodide have the molecular dimeric form in the solid state. Aluminum halides are strong Lewis acids
(see Topic C9) and AlCl3 is frequently used as an acid catalyst, for example, in organic Friedel-Crafts reactions.
 G5—GROUP 13: ALUMINUM TO THALLIUM 203

Complex halides containing the ions [AlF6]3− and [AlCl4]− are easily formed and can be useful for the preparation of
compounds containing unusual cations such as (see Topic G4).
The most stable form of the oxide Al2O3 is α-alumina with the corundum structure where Al3+ ions occupy two-
thirds of the octahedral holes in a hexagonal close-packed oxide lattice. Another form γ-Al2O3 has a defect spinel
structure (see below). So-called β-alumina is in fact a mixed oxide of aluminum of approximate formula NaAl11O17
with a disordered arrangement of Na+ ions, and is a good ionic conductor (see Topic D7).
Aluminum forms many mixed oxides of which the aluminosilicates are major constituents of minerals (see
Topic J2). In these compounds aluminum sometimes replaces a portion of the silicon present as corner-sharing SiO4
groups (see, e.g. zeolites, Topic D5). The mixed oxide mineral spinel MgAl2O4 gives its name to an important
structure type. One-half of the octahedral holes and one-eighth of the tetrahedral holes are filled in a cubic close-packed
array of oxide ions. In the normal spinel form adopted by MgAl2O4 the divalent Mg2+ ion is in tetrahedral sites and
the trivalent Al3+ is octahedral. (See Topic H4 for other examples.) In the defect spinel structure of γ-Al2O3 a fraction
of the cation sites are occupied at random.
Halides and oxides of Ga and In are fairly similar to those of Al, but have less negative enthalpies of formation and
(with In) a tendency to higher coordination. TlIII is more strongly oxidizing; for example, there is no TlIII iodide, and
the compound of stoichiometry TlI3 in fact contains Tl1 with the linear tri-iodide ion I3− (see Topic F9).
Al, Ga and In form tetrahedrally coordinated solids with elements of group 15, which are part of the series of III–V
semiconductors (i.e. groups 13–15, III–V in old nomenclature; see Topic A4). The mixed compounds gallium
aluminum phosphide Ga1−xAlxP and the arsenide Ga1−xAlxAs are used for light-emitting diode (LED) displays and
semiconductor lasers.
Aluminum hydride AlH3 has a structure similar to that of AlF3. The tetra-hydroaluminate ion [AlH4]− is a powerful
reducing and hydride transfer agent, generally used in the form of lithium aluminum hydride’ LiAlH4 made by reaction
of LiH with AlCl3. Stability of hydrides decreases down the group but [GaH4]− is fairly stable and the unstable
digallane molecule Ga2H6 has been identified with a structure like that of diborane (see Topic C1, Structure 16).
Organoaluminum compounds are dimeric but the bonding is different from that of halides as the bridging
methyl groups in Al2(CH3)6 (1) must be held by three-center two-electron bonds similar to those in diborane (see
Topic C7). Organometallic compounds of Ga, In and Tl are less stable than for Al and do not dimerize.

Lower oxidation states

Gas-phase molecules such as AlH, AlCl and AlO are known at high temperatures and low pressures but, as in group 2,
disproportionation occurs under normal conditions because of the much higher lattice or solvation energies associated with
M3+ (see Topics D6 and G1). As these energies decrease with ion size down the group, the tendency to
disproportionation also declines, and lower oxidation states become commoner. Figure 1 shows the possibility of
forming In+ and Tl+, the former prone to disproportionation, the latter much more stable. The increasing stability of
ions with the (ns)2 configuration in lower periods is often called the inert-pair effect. It is particularly marked in
period 6 because of the high ionization energies of these elements (see PbII, Topic G6) but it is important to remember
that it depends not on ionization energies alone but on a balance of different energy trends.
Volume 2 - Nomor 1, Oktober, 2019 (39-46)
ISSN: 2622-7851, e-ISSN: 2622-786x
Available online at http://ejournal.unmus.ac.id/index.php/science
DOI: 10.35724/mjose.v2i1.2244

Analisis Kandungan Aluminium Dalam Kaleng Bekas Untuk Pembuatan Tawas

Novike Bela Sumanik, John Yoro Parlindungan, Rosalinda Zeniona Maarebia

Jurusan Pendidikan Kimia, Fakultas Keguruan dan Ilmu Pendidikan,

Universitas Musamus, Merauke, Indonesia

novikebela@gmail.com

Received: 25th July 2019; Revised: 27th August 2019; Accepted: 30th September 2019

Abstak Tujuan Penelitian ini untuk menganalisis kandungan aluminium dari kaleng bekas minuman
yang merupakan limbah masyarakat. Kaleng bekas yang digunakan pada penelitian ada 4 jenis yaitu
bear brand (putih), yeos cincau, larutan penyegar cap kaki 3 serta milo. Penelitian ini menggunakan
metode sebagai berikut menyiapkan sampel, preparasi bahan, pelarutan, pengendapan, pemanasan,
pengenceran, pencucian dan pengeringan. Analisis kadar aluminium menggunakan ICP OES. Hasil
penelitian didapatkan bahwa kandungan aluminium pada kaleng bekas (A) bear brand = 166 ppm,
(B) kaleng bekas yeos =11.739 ppm, (C) kaleng bekas larutan cap kaki tiga =13.962 ppm, (D)
kaleng bekas milo =14.819 ppm. Tawas yang didapatkan dari 1 g kaleng (A) bear brand =
0,2456 gram, (B) kaleng bekas yeos =5,5925 gram, (C) kaleng bekas larutan cap kaki tiga =
8,6903 gram, (D) kaleng bekas milo =12,3208 gram.

Kata Kunci: aluminium, kaleng bekas, tawas.

ANALYSIS OF ALUMINUM CONTAIN OF USED CANS FOR MAKING OF ALUM

Abstract The purpose of this study was to analyze the aluminum content of used beverage cans that
are community waste. There are 4 types of used cans used in this research, namely bear brand
(white), yeos cincau, larutan penyegar cap kaki 3 and milo. This study uses the following methods for
preparing samples, preparation of materials, dissolution, precipitation, heating, dilution, washing
and drying. Analysis of aluminum content using ICP OES. The results showed that the aluminum
content in used cans ranged between 166 ppm and 14,819 ppm. In 1 gram of alum produced 0.2456
ppm to 12.3208 ppm depending on the type of can used.

Keywords: aluminium, used can, alum

 Musamus Journal Science Education, 2 (1), Oktober 2019-41

Alumunium merupakan senyawa yang Pemanfaatan kaleng bekas telah dilakukan

terbentuk dari ion alumunium yang beberapa penelitian terdahulu diantaranya
menghasilkan garam tak berwarna. Garam- memanfaatkan kaleng bekas sebagai
garam rangkap dari alumunium bereaksi koagolan untuk penjernihan air (Syaiful et
dengan ion sulfat membentuk Kristal yang al., 2014), sebagai penghasil gas hydrogen
dikenal dengan tawas atau alum(Vogel, (Wahyuni, Hakim, & Hasfita, 2016), untuk
1985). Berdasarkan keunggulan pembuatan tawas (Purnawan &
alumunium maka dapat dimanfaatkan pada Ramadhani, 2014). Daur ulang dari kaleng
beberapa sektor industri dan dapat bekas dapat digunakan sebagai alternatiif
dijadikan alternatif dalam menaggulangi hemat energi, mengurangi penggunaan
kelangkaan alumunium dan mengurangi sumber daya alam dan menurangi
limbah kaleng (Mulyadi & Fenima, 2011). timbunan sampah (Nadia, Muhmudah,
Setiartini, Harysetiawan, & Jalaudin,
Limbah minuman kaleng perlu diolah
2014). Energi berperan penting dalam
secara tepat agar tidak mencemari
berbagai aspek aktifitas manusia sehinga
lingkungan, karena limbah anorganik
perlu mendaurulang limbah yang dapat
seperti kaleng bekas dibutuhkan sekitar
meningkatkan nilai ekonomis (Rettob &
400 tahun lamanya agar dapat terurai
Waremra, 2019).
dalam tanah (Syaiful, Jn, & Andriawan,
2014). Mengatasi permasalahan sampah Pembuatan tawas dari kaleng bekas
minuman kaleng yang semakin bertambah berguna untuk proses penjernihan air. Hal
setiap harinya maka diperlukan cara untuk ini juga berkaitan dengan menipisnya
mengontrolnya salah satunya dengan sumber air bersih dalam memenuhi
mengekstrak alumunium yang terkandung kebutuhan manusia akibat sebagian air
dalam kaleng bekas menjadi tawas(Murni, yang tercemar (Syaiful et al., 2014).
2017). Mengingat produksi berbagai macam
merek minuman kaleng maka diperlukan
Cara memanfaatkan kaleng bekas dengan
penelitian tentang kandungan aluminium
mengkonversi logam alumunium menjadi
pada merek dagang yang berbeda-beda
tawas atau kalium alumunium sulfat.
agar mengetahui potensi tawas yang besar
Tawas merupakan istilah umum yang
untuk dimanfaatkan menjernihkan air.
sering diguakan dan dapat menguraikan
garam rangkap dari logam-logam tertentu
(Ariani & Mahmudah, 2017).

Copyright © 2019, Musamus Journal of Science Education

Print ISSN: 2622-7851, Online e-ISSN: 2622-786x
 Musamus Journal Science Education, 2 (1), Oktober 2019-44

perhitungan pada sampel A Sebagai 3. Pembuatan tawas

berikut: Reaksi yang berlangsung pada pembuatan
Persamaan regresi linear : tawas adalah sebagai berikut:
y = 2,2378x – 1,1511 2Al + 2KOH + 6H2O → 2K[Al(OH)4] + 3H2….(1)
Maka hasil perhitungan yang
KOH 20% yang ditambahkan pada reaksi
didapat:
bertujuan untuk mempercepat reaksi dan
= reaksi yang terbentuk bersifat eksoterm
= 1,661 ppm karena menghasilkan kalor. Penambahan
Pengenceran dilakukan 100 kali, sehingga KOH 20% berlebih juga bertujuan untuk
= 1,661 x 100= 166 ppm. menghindari Al(OH)3 terbentuk.
Data pengukuran kandungan aluminium Produk yang dihasilkan pada reaksi (1)
dapat dilihat pada Tabel 3. salah satunya adalah gas H2 dengan
ditandai munculnya gelembung-
Tabel 3. Konsentrasi Aluminium
Kaleng Absorbansi (ppm) Konsentrasi (ppm)
gelumbung gas. Saat alumunium bereaksi
A 2,5651 166 semua maka gelembung gas H2
B 261,54 11.739
menghilang. Pemanasan pada tahap ini
C 311,29 13.962
D 330,46 14.819 bertujuan untuk mempercepat reaksi.
Penambahan H2SO4 (6M) pada filtrat dan
Berdasarkan tabel 3 menunjukkan bahwa proses penyaringan berguna untuk
kandungan aluminium pada sampel A menghilangkan pengotor-pengotor yang
lebih sedikit dibandingkan sampel B,C dan terbentuk. Reaksinya sebagai berikut:
D. Urutan kandungan aluminium pada 2K[Al(OH)4]+H2SO4→2Al(OH)3+K2SO4+2H2O….(2)
sampel kaleng bekas sebagai berikut D >
H2SO4 yang ditambahkan berguna dalam
C>B>A. Kandungan setiap sampel
mereaksikan seluruh senyawa secara
berbeda-beda hal ini dikarenakan
sempurna membentuk K[Al(OH)4].
kandungan aluminium setiap jenis kaleng
Produk yang terbentuk Al(OH)3 bereaksi
berbeda, hal ini sejalan dengan penelitian
dengan H2SO4, maka reaksi yang
(Manurung & Ayuningtyas, 2010).
terbentuk:
Berdasarkan kandungan aluminium pada
2Al(OH)3 + 3H2SO4→ Al2(SO4)3 + 6H2O…(3)
masing- masing sampel kaleng bekas maka
semua sampel bisa digunakan. Penambahan H2SO4 berlebih pada reaksi
(3) melarutkan Al(OH)3 dan membentuk
Al2(SO4)3 berupa larutan bening. Produk
Copyright © 2019, Musamus Journal of Science Education
Print ISSN: 2622-7851, Online e-ISSN: 2622-786x
Vogel's
Qualitative Inorganic Analysis

Seventh Edition

Revised by
G. Svehla PhD, DSC, FRSC
formerly Professor of Analytical Chemistry.
University Col/ege. Cork

199712 4692
543.062 VOG Ivog 17

11111111111111111111111111111
1000092118

~LONGMAN
 U."F. GO.
aUU10TI<lA CIlIlITRAL

(OJ. L3~
N~. ltbS2!31
VALOit (SC),O [)
DATA I ?:IJ2
(
{}> ± -.--,~

Addison Wesley Longman Ltd

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First published under the title A Text-book of Qualitative Chemical Analysis 1937
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Qualitative Analysis 1945
Fourth edition under the title A Text-book of Macro and Semimicro Qualitative Inorganic
Analysis 1954
Fifth edition 1979
Sixth edition under the title Vogel's Qualitative Inorganic Analysis 1987
Seventh edition 1996
Reprinted 1997

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3.23 Reactions of the cations

Distinction of Fe(ll) 15. Distinctive tests for iron (II) and iron (III) ions iroo(II) can be detected
and Fe(lll) most reliably with 2,2'-bipyridyl (cf. reaction 9, Section 3.21); the test is
conclusive also in the presence of iron(III). In turn, iroo(III) ions can be
detected with ammonium thiocyanate solution (cf. reaction 11). It must be
remembered that even freshly prepared solutions of pure iron(II) salts
contain some iron(lII) and the thiocyanate test will be positive with these.
If however iron(III) is reduced by one of the ways described in reaction 13,
the thiocyanate test will be negative.
16. Atomic spectrometric tests these have been described in Section 3.21,
reaction 12.
Dry tests 17. Dry tests
(a) Blowpipe test when iron compounds are heated on charcoal with
sodium carbonate, grey metallic particles of iron are produced; these are
ordinarily difficult to see, but can be separated from the charcoal by means
of a magnet.
(b) Borax bead test with a small quantity of iron, the bead is yelIowish-
brown while hot (and yellow when cold) in an oxidizing flame, and pale green
in a reducing flame; with large quantities of iron, the bead is reddish-brown in
an oxidizing flame.

3.23 Aluminium, AI (Ar: 26.98)

Aluminium is a white, ductile and malIeable metal; the powder is grey. It

melts at 659°C. Exposed to air, aluminium objects are oxidized on the
surface, but the oxide layer protects the object from further oxidation.
Dilute hydrochloric acid dissolves the metal readily, dissolution is slower
in dilute sulphuric or nitric acid:
2Al + 6H+ --+ 2AI3+ + 3H 2 i
The dissolution process can be speeded up by the addition of some
mercury(II) chloride to the mixture. Concentrated hydrochloric acid also
dissolves aluminium:
2Al + 6HCl --+ 2A1 3+ + 3H 2 i + 6Cl-
Concentrated sulphuric acid dissolves aluminium with the liberation of
sulphur dioxide:
2Al + 6H 2 S04 --+ 2A1 3+ + 3S0~- + 3S0 2 i + 6H 2 0
Concentrated nitric acid renders the metal passive. With alkali hydroxides a
solution of tetrahydroxoaluminate is formed:
2Al + 20H- + 6H 20 --+ 2[Al(OH)4r + 3H 2i
Aluminium is tervalent in its compounds. Aluminium ions (AI 3+) form
colourless salts with colourless anions. Its halides, nitrate, and sulphate are
water-soluble; these solutions display acidic reactions owing to hydrolysis.
Aluminium sulphide can be prepared in the dry state only, in aqueous
118
 Aluminium(llI) 3.23

solutions it hydrolyses and aluminium hydroxide, AI(OHh, is formed.

Aluminium sulphate forms double salts with sulphates of monovalent
cations, with attractive crystal shapes; these are called alums.

AI (III) reactions Reactions of aluminium(III) ions Use a O.33M solution of aluminium

chloride, AICl 3, or a O.166M solution of aluminium sulphate,
AI 2 (S04k 16H20, or potash alum, K 2S04 . AI 2 (S04k24H 20, to study
these reactions.
NH3 I. Ammonia solution white gelatinous precipitate of aluminium hydroxide,
1 AI(OH)3, slightly soluble in excess of the reagent. The solubility is decreased
white AI(OHh
in the presence of ammonium salts. A small proportion of the precipitate
passes into the solution as colloidal aluminium hydroxide (aluminium
hydroxide sol): the sol is coagulated on boiling the solution or upon the
addition of soluble salts (e.g. ammonium chloride) yielding a precipitate
of aluminium hydroxide, known as aluminium hydroxide gel. To ensure
complete precipitation the ammonia solution is added in slight excess and
the mixture boiled until the liquid has a slight odour of ammonia. When
freshly precipitated, it dissolves readily in strong acids and bases, but after
boiling it becomes sparingly soluble:
A1 3+ + 3NH3 + 3H 0 -+ AI(OHhl + 3NHt
2

NaOH 2. Sodium hydroxide solution white precipitate of aluminium hydroxide:

1
white AI(OHh A1 3+ + 30H- -+ AI(OHhl
Dissolves in excess The precipitate dissolves in excess reagent, forming tetrahydroxoaluminate
IOns:
AI(OHh + OH- -+ [AI(OH)4r
The reaction is a reversible one, and any reagent which will reduce the
hydroxyl-ion concentration sufficiently should cause the reaction to proceed
from right to left with the consequent precipitation of aluminium hydroxide.
This may be effected with a solution of ammonium chloride (the hydroxyl-
ion concentration is reduced owing to the formation of the weak base
ammonia, which can be readily removed as ammonia gas by heating) or by
the addition of acid; in the latter case, a large excess of acid causes the
precipitated hydroxide to redissolve.
[AI(OH)4r + NHt -+ AI(OH)Jl + NH3 i + H 2 0
[AI(OH)4r + H+ ~ AI(OHhl + H 2 0
AI(OHh + 3H+ 1 ~ AI3+ + 3H2 0
The precipitation of aluminium hydroxide by solutions of sodium hydrox-
ide and ammonia does not take place in the presence of tartaric acid, citric
acid, sulphosalicylic acid, malic acid, sugars, and other organic hydroxy
compounds, because of the formation of soluble complex salts. These
organic substances must therefore be decomposed by gentle ignition or by
evaporating with concentrated sulphuric or nitric acid before aluminium
can be precipitated in the ordinary course of qualitative analysis.
119
 Magnesium(ll) 3.35

Magnesium forms the bivalent cation Mg2+. Its oxide, hydroxide, car-
bonate, and phosphate are insoluble; the other salts are soluble. They taste
bitter. Some of the salts are hygroscopic.

Mg(ll) reactions Reactions ofmagnesium(II) ions To study these reactions a O.5M solution of
magnesium chloride MgCI 6 · 6H 20 or magnesium sulphate MgS0 4 · 7H20
can be used.
NH3 1. Ammonia solution partial precipitation of white, gelatinous magnesium
1 hydroxide:
white Mg(OHh
Mg2+ + 2NH3 + 2H 20 ---> Mg(OHhl + 2NHt
The precipitate is very sparingly soluble in water (l2mgl- 1, Ks =
3.4 x 10- 11 ), but readily soluble in ammonium salts.
NaOH 2. Sodium hydroxide solution white precipitate of magnesium hydroxide,
1 insoluble in excess reagent, but readily soluble in solutions of ammonium
white Mg(OH)2
salts:

(NH 4hC0 3 3. Ammonium carbonate solution in the absence of ammonium salts a white
1 precipitate of basic magnesium carbonate:
white MgC0 3

In the presence of ammonium salts no precipitation occurs, because the

equilibrium

NHt + CO~-;::::! NH3 + HC0 3

is shifted towards the formation of hydrogen carbonate ions. The solubility
product of the precipitate being high (Ks of pure MgC0 3 is I x 10- 5 ), the
concentration of carbonate ions necessary to produce a precipitate is not
attained.
Na2C03 4. Sodium carbonate solution white, voluminous precipitate of basic car-
1 bonate (cf. reaction 3), insoluble in solutions of bases, but readily soluble
white MgC0 3
in acids and in solutions of ammonium salts.
Na2HP04 5. Disodium hydrogen phosphate solution white crystalline precipitate of
1 magnesium ammonium phosphate Mg(NH 4 )P0 4 ' 6H 2 0 in the presence of
white ppt
ammonium chloride (to prevent precipitation of magnesium hydroxide)
and ammonia solutions:

The precipitate is sparingly soluble in water, soluble in acetic acid and in

mineral acids. The precipitate separates slowly from dilute solutions because
of its tendency to form supersaturated solutions; this may usually be over-
come by cooling and by rubbing the test-tube or beaker beneath the surface
of the liquid with a glass rod.
153
Received: 2 September 2018 Revised: 2 October 2018 Accepted: 2 October 2018
DOI: 10.1002/er.4276

RESEARCH ARTICLE

Synergistic effect of the fresh Co, Ni, and anion ions on

aluminum or magnesium with water reactions

Xiuman Wang1,2 | Qian Zhang1,2 | Xiaofeng Shi1,2 | Ning Wang3 | Yujun Chai1,2

1
College of Chemistry and Materials
Science, Hebei Normal University,
Shijiazhuang, China
2
National Demonstration Center for
Experimental Chemistry Education, Hebei
Normal University, Shijiazhuang, China
3 water in CoCl2 and NiCl2, producing high amount of H2 without induction
Analysis and Testing Centre, Hebei
Normal University, Shijiazhuang, China
Correspondence
Y. J. Chai, College of Chemistry and
Materials Science, Hebei Normal
University, Shijiazhuang, China.
Email: yjchaiwn@gmail.com;
hebsjz407@163.com
Funding information
Department of Education of Hebei Province,
Grant/Award Numbers: QN2015224,
ZD 2016081
Summary
To analyze the effect of Co and Ni on hydrogen generation in water, the reac-
tions of Mg and Al with water in CoCl2 and NiCl2 solutions are studied in
terms of amount of H2 produced and rate of reaction. Mg rapidly reacts with
time. While there is a short induction time is detected for Al─H2O reaction
in CoCl2 and NiCl2. In addition to the galvanic cell behavior of the Mg (Al)/
Co (Ni) compounds formed, Co and Ni catalyze the hydrogen production reac-
tion; however, the agglomeration of Co or Ni leads to a noticeable decrease in
H2 production. The open‐circuit potential in CoCl2 and NiCl2 solutions after
the addition of Mg or Al at ambient temperature shows an obvious change,
coinciding with the initiation of the hydrogen generation process. Mg rapidly
reacts with water in Co (Ac)2, CoSO4, Ni (Ac)2 and NiSO4 solutions as a conse-
quence of its intrinsic metallic properties and of the formation of Co or Ni. The
hydrogen production amount is lower (<200 ml g−1) in Co (NO3)2 and Ni
(NO3)2, even after adding NaCl. No reaction occurs when adding Al in CoSO4,
Co (Ac)2, Co (NO3)2, NiSO4, Ni (Ac)2, and Ni (NO3)2. The synergistic effect of
Co, Ni, and anion ions in water affects the rate of Al or Mg corrosion and
hydrogen generation.

KEYWORDS
aluminum, hydrogen generation, hydrolysis reaction

1 | INTRODUCTION Mg─H2O reactions, typically considering the addition of

Hydrogen has attracted attention as a renewable energy
source due to its environmental friendliness and high cal-
orific value. Many methods have been used to produce
hydrogen.1-3 Among these strategies, the reaction
between metal and water could represent a valid tech-
nique for in situ hydrogen production. The drawback is
that no hydrogen is produced by the reaction of Al or
Mg with pure water at ambient temperature due to the
formation of an oxide film, which must be destroyed to
allow the Al─H2O or Mg─H2O reactions to occur. Several
studies have been carried out to accelerate the Al─H2O or
OH− ions4,5 or a salt solution,6 ball milling7 the reactants,
or the preparation of alloys.8-10 All of these methods
accelerate hydrogen generation and Al/Mg corrosion.
The hydrogen generation amount and reaction rate
are effectively improved by varying the properties of
water. Owing to the formation of a galvanic cell,
Mg─CoCl2,11 Mg─AlCl3,12 and Mg─FeCl3,13 prepared
by ball milling could rapidly react with water and exhibit
a high conversion and hydrogen generation rate during
the first minute. Hydrogen is produced by the reaction
of Al foil with water in NaCl + CuSO4 solution through
the contact corrosion effect between Al and Cu.14 On

430 © 2018 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/er Int J Energy Res. 2019;43:430–438.
432 WANG ET AL.

FIGURE 2 Effect of the concentration

of CoCl2 and NiCl2 on Mg─H2O/Al─H2O
reaction. (A and B) Mg─H2O reaction in
CoCl2 and NiCl2 and (C and D) Al─H2O
reaction in CoCl2 and NiCl2 [Colour figure
can be viewed at wileyonlinelibrary.com]

TABLE 1 Typical parameters of Mg─H2O and Al─H2O reaction

Concentration Reaction Rate H2 Volume Yield pHa pHb

M (mol L−1) v (ml g−1 min−1) V (ml g−1) Y (%)

Mg‐CoCl2 0.2 25 638 63.2 5.2 8.7

Mg‐NiCl2 1.0 45 960 95.0 4.7 6.6
Al‐CoCl2 1.5 10 1073 78.9 4.5 3.9
Al‐NiCl2 2.5 11 930 68.4 4.1 3.3
a
pH means the pH of salt solution before adding Mg or Al.
pHb presents the pH after Mg─H2O or Al─H2O reaction

The Al corrosion was related to the hydration of its
oxide film with OH− ions, which is reported by Deng.19,20
In this solution, it is possible that Cl− ions not OH− ions
attacked the oxide film and produced pitting, destroying
the oxide film on the surface of Al and Mg. Meanwhile,
Mg or Al was oxidized, while the Co2+ and Ni2+ ions
were reduced to metallic Co and Ni, according to Equa-
tions 1 and 2.
2Al þ 3Co2þ ¼ 2Al3þ þ 3Co
Mg þ Co2þ ¼ Mg2þ þ 3Co
The Co or Ni contacted with Mg or Al and formed Mg
(Al)/Co and Mg (Al)/Ni micro galvanic cells in the salt
solution, which further accelerated the rapid corrosion
of Mg and Al and enhanced the hydrogen generation.
Paul et al reported that hydrogen could generate when
water contacted with a clean Al surface.21 The freshly
generated Ni and Co showed the higher activity, which
favored the production of hydrogen. It was further proved
in Section 2. Following the Mg─H2O reaction, the pH of
the solution increased from ~6 to ~10 due to the produc-
tion of the scarcely water‐soluble Mg (OH)2. On the other
hand, the─H2O reaction caused a decrease in pH to
values ranging between 2 and 4 because of the hydrolysis
(1) of AlCl3 and the complexation reaction of the Al3+ ions.
These changes affected the behavior of the system for fur-
ther additions of Al or Mg (Figure SS1).
Among above mentioned factors, the morphology of
(2) Co and Ni was varying with the concentration of CoCl2
or NiCl2. Therefore, it is necessary to analyze the relation-
ship between the microstructure of Co and Ni and
Mg─H2O/Al─H2O reaction. The formed Co and Ni were
magnetically adsorbed on magnetic bar and were washed
with pure water and ethanol for 5 times, respectively.
WANG ET AL.
cases, the initial reaction rate showed a marked increase
after adding NaCl, illustrating the synergistic effect of
Co and the anions on hydrogen generation. The hydro-
gen generation rate decreased to 27.5 ml g−1 min−1 after
adding Mg in NiSO4, with H2 amount of 755 ml g−1
(Figure 5E). The increased H2 amount of ~100 ml g−1
was detected after adding NaCl. A similar behavior
was observed in Ni (Ac)2, where the H2 amount was
775 ml g−1 (Figure 5F). In Ni (NO3)2 solution, the H2
amount was only 163 ml g−1 without formation of Ni
particles, similarly to what was observed with Co (NO3)2
(Figure 4G). These results showed that the fresh Co or
Ni had a stronger effect on hydrogen generations than
the anion in the NiCl2 solution. The order of the strength
with which the anions favor the hydrogen production
reaction was therefore Ac−~Cl− > SO42− > NO3−.
When immersing Al into solutions including CoSO4,
Co (NO3)2, Co (Ac)2, NiSO4, Ni (NO3)2, and Ni (Ac)2, no
hydrogen was produced because of the presence of the
dense oxide film on the Al surface. On the other hand,
the formation of Co particles on the magnetic bar was
easily observable, confirming the preferential occurrence
of the reaction between Al and Co2+, coinciding with
the change of open potential. Small amounts of H2
(<200 ml g−1) in the CoSO4 (NiSO4,) and Co (Ac)2 (Ni
(Ac)2) solutions were detected after the addition of higher
amounts of NaCl or salt (Figure S4), as shown in Table 2,
which were still significantly lower than the quantities
obtained in the CoCl2 solution. SEM images of Co in Co
(Ac)2 and CoSO4, shown in Figure 6A and 6B,
respectively, showed the obvious agglomeration of the
plate‐shape particles. On the contrary, the particles
tended to disperse in CoCl2 (Figure 5C). This observation
showed that the morphology of Co or Ni, as well as that
of the anions, had a significant effect on the Al─H2O
reaction. No hydrogen or Co was detected in the
1.5 mol L−1 Co (NO3)2+6 mol L−1 NaCl and 1.5 mol L−1
Ni(NO3)2+6 mol L−1 NaCl solutions, suggesting the slow
kinetics between Al and Co2+ ions. Combining the results
of the Al and Mg reactions in salt solutions, it can be
concluded that the cooperation of Co, Ni, and anions
affected the Al and Mg corrosion and hydrogen generation
reactions.
4 | CONCLUSIONS
The effect of Co or Ni and anions on Mg/Al─H2O reaction
was investigated. Hydrogen was rapidly produced after
adding Mg or Al to an aqueous CoCl2 solution due to the
synergistic reaction of the pitting of Cl− ions, the
microgalvanic cells, and the active Co or Ni formed by
oxidization/reduction reaction. For increasing CoCl2
437
concentrations, the amount of H2 produced underwent
an initial rise (x = 0.50‐1.0 mol L−1), followed by a decrease
(>1.0 mol L−1). This was regarded as the agglomeration of
Co or Ni, which reduced the catalyst activity. The change
of the open‐circuit potential coincided with the Mg or Al
corrosion and hydrogen generation. Mg quickly reacted
with water in Co (Ac)2, CoSO4, Ni (Ac)2, and NiSO4 but
only low hydrogen was detected in Co (NO3)2 and Ni
(NO3)2. Small amounts of hydrogen were also measured
after adding Al to the same solution, even under condi-
tions of high NaCl concentrations (<200 ml g−1). The
results showed that Co, Ni, and the anions affected the
Al or Mg corrosion and hydrogen generation.
ACKNOWLEDGEMENTS
This work was supported by the fund of Department of
Education of Hebei Province (QN2015224 and ZD 2016081).
ORCID
Yujun Chai http://orcid.org/0000-0002-5772-3854
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