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Analisis gravimetri

Prinsip Dasar Analisis


Gravimetri
Salah satu metode analisis kuantitatif makro yang
paling akurat
Analit (bahan yang dianalisis) secara selektif
dikonversi menjadi endapan yang stabil (tidak
larut)
Pengukuran massa endapan
Mengubungkan massa endapan dengan masa
analit
Masih banyak digunakan dan sering lebih akurat

Contoh
Sampel garam dapur (NaCl)
Larutan sampel ditambah larutan perak nitrat,
endapan terbentuk adalah perak klorida
(AgCl)
Cl- + Ag+ AgCl(s)

Langkah-langkah umum
1.
2.
3.
4.
5.
6.
7.
8.
9.

Sampel kering ditimbang dengan akurat


Penyiapan larutan
Pengendapan
Penyempurnaan endapan (digestion)
Peyaringan
Pencucian
Pengeringan atau pembakaran (ignition)
Penimbangan
Perhitungan kadar

Konversi analit menjadi endapan


Pengendapan secara kuantitatif dengan perekasi
yang sesuai
Penguapan dan pengumpulan endapan
Tanpa kehilangan massa selama penanganan
dan proses
Bebas dari pengotor dan pelarut

Penentuan massa
Langsung (BaSO4, AgCl, dll)
Selisih (CaC2O4.H2O dikonversi menjadi
CaC2O4.)

Langkah penting

Teknik Pengendapan
Penyiapan pereaksi untuk mengendapkan analit
Mereaksikan analit menjadi senyawa atau unsur yang
tidak larut
Endapan mempunyai komposisi yang telah diketahui
(atau bisa diubah menjadi senyawa atau unsur yang
komposisinya diketahui)

Perlakuan endapan
Pengumpulan endapan secara kuantitatif (tidak ada
yang hilang)
Isolasi produk murni

Menimbang massa
Menghitung kadar analit awat (konsentrasi)

Endapan yang akan ditimbang


Siap disaring dan dimurnikan
Kelarutan sangat rendah
Stabil (tidak mudah bereaksi, misalnya
oksidasi)
Komposisi diketahui setelah pengeringan atau
pembakaran (ignition)

Agen pengendapan

Selektif
Ag+ + Halida (X-) AgX(s)
Ag+ + CNS- AgCNS(s)
Spesifik
Dimethylglyoxime (DMG)
2 DMG + Ni2+ Ni(DMG)2(s) + 2 H+

Endapan bisa disaring


Suspensi koloidal
Partikel berdiameter 10-7 sd 10-4 cm
Biasanya sulit mengendap
Sukar untuk disaring

Suspensi kristalin
Diameter > (1/10) mm
Secara spontan mengendap
Mudah disaring

Gravimetric Analysis
Kemudahan endapan untuk disaring:
Pembentukan endapan dikendalikan oleh
supersaturasi relatif (RELATIVE
SUPERSATURATION disingkat R.S.)

R.S. = (Q-S)/S
S = Kelarutan pada saat kesetimbangan (dari
Ksp)
Q = Konsentrasi sesaat

Semakin besar Q akan mengarah ke


suspensi koloid

Faktor penting dalam analisis gravimetri

Nukleasi
Ion/atom/molekul bergerombol (bergabung membentuk inti
endapan)

Pertumbuhan kristal

Nukleasi

Kondensasi ion/atom/molekul dengan inti endapan yang ada


membentuk partikel lebih besar yang kemudian mengendap

Endapan koloid
Partikel koloid masih tertinggal tidak mau mengendap (suspended)
karena terjadi penyerapan ion sehingga memiliki muatan (+) atau
(-)

Pertumbuhan kristal

Ilustrasi pertumbuhan kristal

Suspensi koloid

Foto pertumbuhan kristal

Faktor penting dalam analisis gravimetri


Koagulasi, aglomerasi
Endapan partikel menyatu (begabung) membentuk
partikel lebih besar, bisa difilter (dalam elektrolit
inert)

Peptizasi
Pelarutan kembali koloid dengan pencucian dan
pemisahan elektrolit inert

Koagulasi koloid

Gambar ini menunjukkan


bahwa koloid yang
mengalami koagulasi
permukaannya yang luas
terus kontak dengan larutan
dimana kolid ini terbentuk
Bawah koloid Al(OH)3

Pengaruh suhu pada massa endapan

Faktor penting dalam analisis gravimetri


Ko-prespitasi
Umumnya senyawa yang terlarut mengendap bersama
dengan endapan yang diinginkan (adsorpsi permukaan,
oklusi, inklusi, campuran kristal, terperangkap),
Misalnya ion nitrat terperangkap dalam endapan AgCl

Penghancuran (Digestion)
Precipitation heated for hour(s) in contact with solution
form which it was formed

Lihat ilustrasi di bawah

Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Gb Ilustrasi Ostwald ripening

Lihat proses terbentuknya adsorpsi ion di bawah

Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Gb Representasi partikel AgCl dan penyerapan ion

Bebarapa senyawa yang bisa digunakan untuk


mengendapkan analit

Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Analisis elektrogravimetri.
Analisis ini mendasarkan teknik
pengendapan dengan menggunakan
potensial searah (DC). Pada potensial
reduksi tertentu (sesuai dengan potensial
reduksi standar), ion logam diendapkan
pada katoda. Endapan yang ada pada katoda
adalah berat kuantitatif unsur tersebut di
dalam sampel. Perhitungan kadar bisa
dilakukan dengan mudah.

Perhitungan dalam analisis gravimetri


memerlukan skill
Pengetahuan reaksi kimia
Stoikiometri
Komposisi kimia endapan

Examples of calculations (for tutorial)


Gravimetric factor(GF)-the weight of
analyte per unit weight of precipitate
f wt analyte (g/mol)
a
GF
( mol analyte/mol precipitate)
f wt precipitate (g /mol) b
g analyte/g precipitate

So, if Cl2 in a sample is converted to chloride and


precipitated as AgCl, the weight of Cl2 that gives 1 g of
AgCl is
f wt Cl2 (g Cl2/mol Cl2)
1
g Cl2 g AgCl
( mol Cl2/mol AgCl)
f wt AgCl (g AgCl/mol AgCl ) 2
g AgCl GF (g Cl2/g AgCl)
g AgCl 0.2473 7 (g Cl2/g AgCl)

Example 1
calculate the grams of analyte per gram of precipitate for the
following conversion:
Analyte

P
K2HPO4

Bi2s3

Precipitate

Ag3PO4
Ag3PO4
3BaSO4

Solution

at wt P (g/mol)
1
g P/g Ag 3 PO 4
( mol P/mol Ag 3 PO 4 )
g wt Ag 3 PO 4 (g/mol)
1
30.97 (g P/mol )
1

418.58 ( g Ag 3 PO 4 /mol) 1
0.07399 g P/g Ag 3 PO 4 GF

f wt K2HPO4 (g/mol) 1
g K2HPO4/g Ag3PO4
( mol K2HPO4/mol Ag3PO4)
f wt Ag3PO4 (g/mol) 1
174.18 (g K2HPO4(g/mol ) 1

418.58 ( g Ag3PO4/mol) 1
0.41612 g K2HPO4/g Ag3PO4 GF
f wt Bi2S3 (g/mol) 1
g Bi2S3/g BaSO4
(mol Bi2S3/mol BaSO4)
f wt BaSO4 (g/mol) 3
514.15 (g Bi2S3/mol) 1

233.40 (g BaSO4)
3
0.73429 g Bi2S3/g BaSO4 GF

In order to calculate the percent composition by


weight of analyte in the sample, the weight of
substance sought was divided with the weight of
sample and times with 100%.
The weight of sample sought can be obtain from
the weight of precipitate and the corresponding
weight/mole relationship, as in equation below:
Weight of substance sought (g) Weight of precipitate(g)
f wt substance sought (g/mol)

f wt precipitate (g/mol)
a
( mol substance sought/mol precipitate)
b
Weight of precipitate (g) GF (g sought/g precipitate)

Thus, the general formula would be:


% sought

weight of precipitate (g) GF (g sought/g precipitate)


100%
weight of sample (g)

Example 2
An ore is analyzed for the manganese content by converting the manganese
to Mn3O4 and weighing it. If a 1.52g sample yeilds Mn3O4 weighing
0.126g,what would be the percent Mn2O3 in the sample? The percent Mn?
Solution:
3Mn 2 O 3
(g Mn 2 O 3 / g Mn 3 O 4 )
2Mn 3 O 4
% Mn 2 O 3
100%
1 . 52 g sample
0.126 g 3(157.9)/2 (228.8)

100% 8.58%
1 . 52 g
0.126 g Mn 3 O 4

3Mn
( g Mn/ g Mn 3 O 4 )
Mn
3O 4
% Mn
100%
1.52 g sample
0.126 g 3(54.94)/2 28.8

100% 5.97%
1 . 52 g
0.126 g Mn 3 O 4

Example 3
What weight of pyrite ore (impure FeS2 ) must be taken for analysis so that
the BaSO 4 precipitate weight obtained will be equal to one-half that of the
percent S in the sample?

Solution:
gA
100%
g sample
1
S
A(g BaSO4)
(g S/g BaSO4)
BaSO4
A %S 2
100%
g sample
1 32.064

2
233.40 100%
1% S
g sample
g sample 6.869g
%A

Soal-soal latihan

What is the %KCl in a solid if 5.1367 g of solid gives rise to 0.8246 g AgCl?
The calcium in a 200.0 mL sample of a natural water was determined by
precipitating the cation as CaC2O4. The precipitate was filtered, washed, and
ignited in a crucible with an empty mass of 26.6002 g. The mass of the
crucible plus CaO (fwt 56.077 g/mol) was 26.7134 g. Calculate the
concentration of Ca (fwt 40.078 g/mol) in the water in units of grams per
100 mL.
An iron ore was analyzed by dissolving a 1.1324 g sample in concentrated
HCl. The resulting solution was diluted with water, and the iron(III) was
precipitated as the hydrous oxide Fe2O3.xH2O by addition of NH3. After
filtration and washing, the residue was ignited at high temperature to give
0.5394 g pure Fe2O3 (fwt 159.69 g/mol). Calculate (a) the % Fe (fwt 55.847
g/mol) and (b) % Fe3O4 (fwt 231.54 g/mol) in the sample.
A 0.2356 g sample containing only NaCl (fwt 58.44 g/mol) and BaCl2 (fwt
208.23 g/mol) yielded 0.4637 g of dried AgCl (fwt 143.32 g/mol). Calculate
the percent of each halogen compound in the sample.

Soal-soal latihan

A mixture containing only Al2O3 (FM 101.96) and Fe2O3 (FM 159.69)
weighs 2.019 g. When heated under a stream of H2, Al2O3 is
unchanged, but Fe2O3 is converted into metallic Fe plus H2O (g). If
the residue weighs 1.774 g, what is the weight percent of Fe2O3 in the
original mixture?

An ore is analyzed for the manganese content by converting the


manganese to Mn3O4 and weighing it. If 1.52-g sample yields Mn3O4
weighing 0.126-g, what would be the percent Mn2O3 in the sample?
The percent Mn? Molar mass: Mn2O3=157.9; Mn3O4= 228.8;
Mn=54.94
Orthophosphate (PO33-) is determined by weighing as ammonium
phosphomolybdate, (NH4)PO4.12MoO3. Calculate the percentage P
and P2O5 if 1.1682-g precipitate ere obtained from a 0.2711-g sample.
Molar mass: (NH4)PO4.12MoO3 =1876.5; P2O5= 141.95; P=30.97

Soal-soal latihan

The Aluminum in a 0.910g sample of impure ammonium aluminum sulfate was


precipitated with aqueous ammonia as the hydrous Al2O3.xH2O. The precipitate was
filtered and ignited at 1000oC to give anhydrous Al2O3, which weighed 0.2001g.
Express the result of this analysis in terms of: a. % Al2O3 b. % Al in the sample.
An iron ore was analyzed by dissolving a 1.1324-g sample in concentrated HCl. The
resulting solution was diluted with water and iron (III) was precipitated as the hydrous
oxide Fe2O3.xH2O by the addition of NH3. After filtration and washing the precipitate
was ignited to give 0.5394-g of pure Fe2O3 (159.69 g/mol). Calculate the % Fe (55.847
g/mol), % Fe3O4 (231.54 g/mol) in the sample.
The calcium in a 200.0 mL sample of a natural water was determined by precipitating
the cation as CaC2O4. The precipitate was filtered, washed, and ignited in a crucible
with an empty mass of 26.6002 g. The mass of the crucible plus CaO (fwt 56.077
g/mol) was 26.7134 g. Calculate the concentration of Ca (fwt 40.078 g/mol) in the
water in units of grams per 100 mL.
An iron ore was analyzed by dissolving a 1.1324 g sample in concentrated HCl. The
resulting solution was diluted with water, and the iron(III) was precipitated as the
hydrous oxide Fe2O3.xH2O by addition of NH3. After filtration and washing, the residue
was ignited at high temperature to give 0.5394 g pure Fe2O3 (fwt 159.69 g/mol).
Calculate (a) the % Fe (fwt 55.847 g/mol) and (b) % Fe3O4 (fwt 231.54 g/mol) in the
sample.