Kimia Unsur

Gol Utama, Gol Logam transisi,

Lantanida dan Aktinida

Roy Andreas
Kontrak Pembelajaran
Kuliah 2 SKS, 2 jam pertemuan @100 menit per minggu
Deskripsi singkat:
Sejarah dan perkembangan unsur dan kecenderungannya
dalam sistem periodik
Kompetensi:
Setelah mengikuti MK ini mahasiswa dapat menjelaskan
kecenderungan sifat-sifat unsur, senyawaan, kelimpahan,
proses pemurnian. (+ perkembangan terbaru, jika ada)
Outcome:
Critical thinking, membantu tugas akhir, meningkatkan
komunikasi , kerjasama dalam diskusi
References
 Catherine E. Housecroft and Alan G. Sharpe, "Inorganic
Chemistry", 3rd Edition, Pearson.
 James E.Huheey, Ellen A.Keither, Richard L. Keiter. 1993. Inorganic
Chemistry: Principles of Structure and Reactivity 4th Edition. Harper
Collins College, New York.
 Shriver, Atkins, “Inorganic Chemistry,” 3rd Edition, 1999.
 Cotton, F.A., and Wilkinson, G. 1976. Basic Inorganic Chemistry,
3rd ed. NY: John Wiley&Sons, inc.
Grading
 Quizzes : ?
 Tugas Terstruktur : ?
 UAS : ?
(nilai diakumulasi dari kuliah saya dan Bu Tien)

Tidak ada ujian perbaikan! Hubungi saya jika anda

berhalangan, atau sakit (dengan surat dokter).
 Group 1: Hydrogen

Hydrogen is the simplest element, consisting of a single

proton and electron.
It has a reasonably high electro-negativity, which means that
it forms covalent bonds with carbon which has a similar
electronegativity of 2.5.
Once it has ionized to form a proton, it has no remaining
electrons, and, in theory has an ionic radius of zero. In fact,
it is never a bare proton, and always retains some electron
density, but still has a very small size where it is formally
cationic. This gives it a very high charge density, and the
proton is a very strong Lewis acid.
 Perbandingan Li, H dan F
Litium Hidrogen Fluorine
El valensi 1s2 2s1 1s1 2s2 2p5
jari jari atom Å 1.55 0.32 0.72
jari-jari ion 1.16 1.53(H-) 1.19
Å (CN =6) 0.000015(H+)
electronegativitas 1.0 2.1 4.0
(Pauling)
Z/r (r=ionic) 0.86 0.65 (H-) 0.84
67000 (H+)
ked oksidasi +1 +1 (covalent) -1
-1 (ionic)
E. ionisasi Kj/mol 520 1312 1680
Afinitas Elektron -58 -77 -333
Energi ikat X-X … 436.4 150.6
Kj/mol
 Group 1: Hydrogen

Hydrogen has one valence electron like lithium, but is also

one electron short of completing an inert-gas
configuration like fluorine.

This implies hydrogen might have some properties in

common with all three of these elements.

Hydrogen has a “split personality”

This is reflected in the various positions to which
hydrogen is assigned in the periodic table.
Aspek kimiawi  3 tipe elektronik :
- Melepaskan 1 e- valensi  H+
- Menerima 1 e-  ion hidrida (H-) misal : NaH dan CaH2
- Pembentukan pasangan elektron sbg ikatan kovalen
tunggal

Bergantung dari ligan yang ada

Misal BH3 asam lewis, CH4 netral, NH3 basa, H2O basa
atau asam, HF gas, asam lemah
HIDROGEN
 Unsur yang paling banyak berikatan dengan unsur lain
 Densitas paling rendah

 dapat membentuk senyawa Hidrida  dgn unsur

elektropositif
 dapat membentuk senyawa polar  dgn unsur
elektronegatif
 dapat membentuk senyawa non polar  dgn C
HIDRIDA
 „H-H bond energy 436.4 KJmol-1.
 H(g) + e- → H- (g) ∆EA H -76 kj/mol;
 The highest homonuclear single-bond energy known
 Alasan mengapa hidrogen tidak begitu reaktif
 „Ikatan dengan satu unsur lain disebut hidrida biner
 oxidation state hasil reaksi biasanya +1 atau -1.
 Pada logam transisi kadang sukar dikarakterisasi

„
Classes of Hydrides:
1. Ionic Hydrides -contain an H+ ion, formed between H and
electropositive elements.
2. Covalent Hydrides – molecular formed between H and
nonmetals.
3. Metallic Hydrides – formed between transition metals and H
Hidrida Extended Borderline Hidrida
ionik
polymeric covalent hydride Kovalen
hydride

Hidrida metalik

Hidrida metalik
 Hidrida Ionik
 characterized by hydrogen in the -1 state, occur only with
the least electronegative metals, those of Groups 1A and 2A.
 „There is good evidence to show that these compounds
really are significantly ionic.
 ‰Molten ionic hydrides like salts, conduct electricity well,
implying the existence of charged species,
 ‰The melt releases hydrogen at the positive anode upon
electrolysis, consistent with a H- species.
 „Ionic hydrides are usually gray solids formed by direct
combination of the metal and hydrogen at elevated
temperatures, they are used as drying and reducing agents,
as strong bases, and some safe sources of pure hydrogen.
 Hidrida Ionik
 „Calcium hydride CaH2 is particularly useful as a drying
agent for organic solvents, reacting smoothly with water:
CaH2(s) + 2H2O (l) → Ca2+(aq) + 2H2(g) + 2OH-(aq)

 Sodium hydride, NaH, reacts violently with water to

produce H2 gas, H2(g) and hydroxide in solution and like
other ionic hydrides, is a strong base.
 LiH and CaH2 are convenient portable sources of pure
hydrogen.
 LiH also reacts with aluminum chloride to form the
complex hydride LiAlH4, which is extremely useful as a
reducing agent in organic chemistry
1.Hidrida ionik

- terbentuk dgn logam elektropositif (gol

alkali dan alkali tanah) LiH, NaH
- sangat reaktif
LiH (s) + H2O (l)  LiOH(aq) + H2 (g)
- dpt sbg pereduksi
SiCl4 (g) + NaH(s)  SiH4(g) + NaCl(s)
 Hidrida Metalik
 „Hydrogen reacts with a variety of transition metals
including lanthanides, and actinides, to produce a class
of hydride that is rather poorly understood.
 „These brittle solids are generally metallic in appearance,
good conductors of electricity, and of variable
composition.
 „Their hydrogen-metal ratios are often not ratios of small
whole numbers and so they are referred to as
nonstoichiometric compounds. e.g. TiH1.7, TiH2, PdH0.65,
LaH1.86, UH3
 Hidrida Metalik
 „
These metallic hydrides were formerly thought to be interstitial
compounds with atomic hydrogen fitting into the holes
(interstices) left in the crystal structure of the pure metal.
 „In many cases however, the arrangement of the metal atoms in the
hydride has been found to be different from that in the pure
metal.
 „Better models are emerging to propose the correct structures of
these materials but work is ongoing.
 „Metal hydrides have several important applications – the hydrides
are fairly easily formed from a direct combination of hydrogen gas
and the metal. The hydrogen uptake is reversed at higher
temperatures, yielding finely powdered metals and hydrogen gas.
These compounds are a good way to store and purify hydrogen, as
well as to produce finely divided metals.
 „The future for hydrogen – fuel cells
 Hidrida Kovalen
 We learned before that a large charge density leads to a
high polarizing power and a tendency to form covalent
bonds. (Because of the very small radius of this species,
its charge density is extremely large, larger than any
other ionic species).

 „Hydrides can be subdivided into two types: those that

form discrete, self-contained neutral of positively
charged molecular units: for example, HCl, H2O, H3O+,
NH3, NH4+ and those that assume an extended,
polymeric structure, such as AlH3.
 Hidrogen  ditemukan dalam bentuk gas H2
 Gas hidrogen  dalam bentuk molekul diatomik

Sifat-sifatnya :
 Tidak berbau
 Tidak berasa
 Tidak berwarna
Isotop Hidrogen :
- Normal hidrogen
- Deuterium
- Tritium

Isotop Massa Titik didih Energi ikatan

Molar (K) (kJ/mol)
(g/mol)
H2 2,02 20,6 436
D2 4,03 23,9 443
T2 6,03 25,2 447
 The differences in atomic properties carry over to hydrogen
compounds.
 „In D2O, the molecules move slowly at a given temp than H2O
molecules.
 „For example, “heavy water” or deuterium oxide D2O, can be
separated from ordinary water by electrolysis.
 „One reason for this is that the hydrogen ions H+ move to the
negative electrode more rapidly than the twice as heavy
deuterium ions D+.
 „It follows that ordinary hydrogen gas H2, is the preferred
product and the concentration of D20 in the water left
behind increases as the electrolysis is carried out. The
remaining water becomes heavier and heavier and is called
heavy water.
Nama jml symbol massa, % masa
netron u kelimpahan hidup
(tahun)
1
Hidrogen 0 1H 1.00728 99.985
(H) atau
protium
2
Deuterium 1 1H 2.0140 0.015
(D)
3
Tritium (T) 2 1H 3.01605 10-17 12.3
Pembentukan jembatan hidridik  misal pada molekul diboran
(B2H6)
 Hydrogen bonding:
One of the most important properties of the proton is its ability to form H-bonds
when attached to more electronegative donor atoms such as F, O, or N. An H-bond is
judged to be present when the separation between the two atoms forming the H-bond
is less than the sum of the van der Waal’s radii. For H-bonds typical X-H-X
distances between
X atoms are:

O- -H- -O 2.76 Å
F- - H- -F 2.55 Å
N- -H- -N 3.00 Å

Figure 2. Hydrogen bonding of four water molecules around a central water

molecule.
- Pembentukan ikatan hidrogen  jembatan protonik
Akibat
ikatan hidrogen :

Titik didih normal

senyawa
hidrogen blok p
Ion Hidrogen :
- Jika asam kuat (HCl dan HNO3) dilarutkan dalam air  ion H
terhidrat dgn molekul air  ion hidroksonium atau hidronium
 The hydronium ion:
The small proton in aqueous solution forms the linear two-
coordinate [H2O-H-OH2]+ ion, shown below (left). This low
coordination number is expected from the small size of the
proton.

H+

[H(OH2)2]+.4H2O
Preparasi gas hidrogen :
1. Elektrolisis air dgn elektroda Pt/C dan
katalisator elektrolit garam Na2SO4 
mghslkan gas H2 pada katoda dan O2
pada anoda
katoda : 2 H2O (l) +2e-  2OH- (aq) + H2 (g)
anoda : 2 OH- (aq)  H2O (l) + ½ O2 (g) + 2e-

2. Reaksi logam dgn asam  logam hrs

terletak seb kiri H pada deret Volta (deret
elektrokimia)
Fe (s) + 2HCl (aq)  FeCl2 (aq) + H2 (g)
3. Reaksi Logam dan air
2 K (s) + 2H2O (l)  2KOH (aq) + H2 (g)  sangat
hebat dlm air dingin
2 Na (s) + 2 H2O (l)  2NaOH (aq) + H2 (g)  hebat
dlm air dingin
Ca (s) + 2 H2O (l)  Ca(OH)2 (aq) + H2 (g)  tjd dlm
air panas
3 Fe (s) + 4 H2O (l)  Fe2O4 (s) + 4 H2 (g)  dlm uap
air panas dan logam panas
Dalam industri gas H2 diperoleh :

1. Proses Bosch  uap air panas dialirkan melalui C

sbg pereduksi pd temperatur tinggi
C (s) + H2O (g)  CO (g) + H2 (g)
CO (g) + H2O (g)  CO2 (g) + H2 (g)
Gas CO2 dipisahkan dgn mengalirkan camp gas ke dlm
lart. Karbonat  CO2 akan larut
2. Mengalirkan uap air panas ke dlm gas metana dgn katalisator
Ni  kmdn dialirkan melalui katalisator Fe/Cu pada T =
750 oC
750 0C
CH4 (g) + H2O (g) CO (g) + 3 H2 (g)
Ni

CO (g) + H2O (g) 750 0C CO2 (g) + 3H2 (g)

Fe/Cu

Cara memisahkan CO2 dgn mengalirkan dlm lart. K2CO3

K2CO3 (aq) + CO2 (g) + H2O (l)  2 KHCO3 (aq)