Pendahuluan

1. Kimia Farmasi Kuantitatif II merupakan ilmu yang membahas

senyawa kimia obat terutama untuk tujuan pemeriksaan jumlah
atau analisis kuantitatif senyawa obat.
2. Untuk analisis kuantitatif sebelumnya harus sudah diketahui
jenis senyawanya.
3. Secara garis besar senyawa obat dikelompokkan berdasarkan
atom penyusun dan ikatan kimia dalam molekul yaitu:

1. In organik
1. Dibakar mempunyai sisa, terutama berupa
oksida logam
2. Tidak ada ikatan kimia -C-C- dan - C-H
2. Organik
1. Dibakar berubah warna menjadi hitam (carbon),
selanjutnya habis tidak bersisa
2. Ada ikatan kimia -C-C- dan - C-H
 ANALISIS KUANTITATIF

1.Prinsip utama analisis kuantitatif

dikelompokkan menjadi 2 antaraksi terhadap
senyawa uji (analit):

1.Antaraksi Kimia-Kimia
1.Analisis volumetri

2.Antaraksi Kimia-Energi
1.Analis dengan cara spektroskopi.
Sunlight

Although we see sunlight (or white

light) as uniform or homogeneous in
color, it is actually composed of a
broad range of radiation wavelengths
in the ultraviolet (UV), visible and
infrared (IR) portions of the spectrum.
A diagrammatic representation of electromagnetic
radiation.
The wavelength of light.
Velocity of light = frequency x wavelength

or
  wavelength (units of m, cm, m, nm)
  frequency (units of cycles/sec , sec -1 , Herz)
velocity of light v  
velocity of light in vacuum c  
c  3.00  108 m s 1
Light passing through a substance decreases in
intensity as a result of three processes:

1. reflection at phase boundaries (liquid/air,

glass/liquid, etc.). This is caused by
differences in the refractive index of the
different materials through which the light is
passing
2. scattering of light caused by non-homogeneity
of the sample
3. absorbance by atoms or molecules in solution.
 The first is Beer’s law (Figure 1), which
states that ‘the intensity of a beam of
parallel, monochromatic light decreases
exponentially with the concentration of the
absorbing molecules’.
 Beer’s law (named after German chemist
August Beer) can be expressed
mathematically as
where I0 is intensity of light incident on the
sample, I is intensity of light transmitted by the
sample, k is a constant and c is the concentration
of the sample.
Beer’s Law
 which states that the ‘intensity of a beam of
parallel, monochromatic light decreases
exponentially as the light travels through a
thickness of homogeneous medium’,
 Expressed mathematically as
Lambert’s law,

where I and I0 are as before, l is the

thickness of the medium (or path length)
through which the light passes and k is
(another) constant.
 Taking logarithms,

i.e. absorbance is proportional to path length.

These two fundamental equations are so similar that
they can be combined into one relationship, the Beer–
Lambert law or equation, which can be expressed as

Here k is yet another constant, the value of which

depends on the units used for the concentration
term, c, and on the path length, although this is
usually 1 cm.
 P
T 
P0
dan absorbance A, di mana A = log (1/T), terlihat berkurang
cahaya diliwatkan dan bertambah absorbance. Absorban adalah
logaritma dari transmittance berkaitan. Oleh karena itu bila T =
1.00, A = 0,00; bila T = 0.10, A= 1.00; bila T = 0.01, A= 2.00, dst
If the units of concentration are molarity (i.e.
number of moles per litre), then the constant is e
(the Greek letter ‘epsilon’) and is known as the
molar absorptivity, with units of L mol–1 cm–1,
although the units are seldom expressed. e is
equal to the absorbance of a 1 M solution in a cell
of path length 1 cm and is usually a large number,
approximately 10 000–20 000. In this case the
Beer–Lambert equation is written as
When the concentration of the sample is expressed in percentage
weight in volume(%w/v) or g/100 mL, the constant used isA1%, 1
cm, usually written as A1 1, and is called the specific
absorbance, with units of dL g–1 cm–1 although, again, the value
is usually quoted without units. The A1 1 value is very useful in
pharmacy and pharmaceutical analyses where the molecular
weight of the sample may be unknown (e.g. when analysing a
macro-molecule, such as a protein) or where a mixture of several
components is being analysed in the same sample. This gives the
most useful form of the Beer–Lambert equation: Analytical
spectroscopy
 Analisis senyawa Tunggal

E= ε c .d (=koefisien ekstinksi molar, c mol. L-1, d cm)

E = E1cm .c.d (ekstinksi spesifik, c = g/100 ml, d cm)
1%

A = a.b.c ( koefisien ekstinksi, c = g/L, d cm)

 Visible Spectroscopy or Colorimetry

1.Prinsip membandingkan warna larutan sampel

dengan warna larutan pembanding. :

1.Nessler
2.Hehner
3.Duboscq
4.Filter photometer (photoelectric
colorimeter)
5.Spektrophotometer UV-VIS
Hehner
 Duboscq

1. Alat ini digunakan untuk mengukur ketebalan atau panjang

larutan sampel dan standar yang memberikan transmisi yang
sama.
2. Tubes containing the solutions to be compared are mounted
side by side. White light is reflected from a mirror so as to pass
through both tubes.
3. Plungers of fixed length dip into the two solutions and the cups
are raised or lowered until the light passing through the two
solutions appear to be the same.
4. The eyepiece is so arranged that we observe two half circles,
one for each ot the solutions. When the two halves appear
identical, the depth of layer in the two tubes is read from
gradate scales.
5. The concentration of the unknown solution is computed from
the known concentration of the standard and the lengths of the
light paths to give equal transmission, as follows.
This instrument (usually a Duboscq type,
Fig 1) measures the depth or thickness of
sample and standard solutions to give the
same transmission.
1.Filter photometer (photoelectric
colorimeter)

Filt er

pita chj w.hijau

Kaca berwarna
(misal:warna hijau)
A

400 500 550

800
Lamda
A

1 2 3 4 5 6 7 8
Consentration (mg/ml)
Fotosel (Photovoltaic Cell; Barrier Layer Cell).
electron pengumpul

Se (semikonduktor)

Pelat Fe
_
+
At equal transmission we have the relation

A standard = A unknown
This gives the simple relation

b 1c1 = b 2c2
Since c2 is known, that of the standard solution, we have

c1 = b2/b1.c2
 Analisis Kolorimetri

1.Prinsip memnandingkan warna larutan sampel

dengan warna larutan pembanding. :

1.Nessler
2.Hehner
3.Duboscq
 Duboscq

1. Alat ini digunakan untuk mengukur ketebalan atau panjang

larutan sampel dan standar yang memberikan transmisi yang
sama.
2. Tubes containing the solutions to be compared are mounted
side by side. White light is reflected from a mirror so as to pass
through both tubes.
3. Plungers of fixed length dip into the two solutions and the cups
are raised or lowered until the light passing through the two
solutions appear to be the same.
4. The eyepiece is so arranged that we observe two half circles,
one for each ot the solutions. When the two halves appear
identical, the depth of layer in the two tubes is read from
gradate scales.
5. The concentration of the unknown solution is computed from
the known concentration of the standard and the lengths of the
light paths to give equal transmission, as follows.
This instrument (usually a Duboscq type,
Fig 1) measures the depth or thickness of
sample and standard solutions to give the
same transmission.
At equal transmission we have the relation
A standard = A unknown

This gives the simple relation

b1c1 = b2c2
Since c2 is known, that of the standard solution, we have
c1 = b2/b1.c2
Spektrum Absorpsi

1. Semua atom dan molekul mampu menyerap energi

sesuai pada batas-batas tertentu, tergantung pada
struktur dari substansi.

2. Energi dapat dihasilkan dalam bentuk radiasi

elektromagnetik (“light”). Jenis dan jumlah radiasi
terabsorbsi oleh molekul tergantung pada struktur
molekul; juga tergantung pada jumlah molekul yang
berinteraksi dengan radiasi.

3. Studi dari keterkaitan ini disebut spektroskopi absorpsi

“absorption spectroscopy”
At equal transmission we have the relation

A standard = A unknown
This gives the simple relation

b 1c1 = b 2c2
Since c2 is known, that of the standard solution, we have

c1 = b2/b1.c2
R1 R1
C O C O
R2 R2

transisi π → π*

R1 R1
C O C O
R2 R2
transisi n → π*
 H4*

H3
X Y
H2
H

H1
  wavelength (units of m, cm, m, nm)
  frequency (units of cycles/sec , sec -1 , Herz)
velocity of light v  
velocity of light in vacuum c  
c  3.00  108 m s 1
 Absorption Spectra of Mixtures
Containing n components

A1  a1 bc1  a1 bc2  a1 bc3      a1 bcn

A2  a2 bc1  a2 bc2  a2 bc3      a2 bcn

An  an bc1  an bc2  an bc3      an bcn
Chromophores
To describe the system containing the
electrons responsible for the absorption.

Tabel: The Absorption of Simple Unconyugated

Chromophore
Tabel: The Absorption of Simple Unconyugated Chromophore

C C n – σ* 150 nm
Gambar: Plot Hk Beer pada Theophyllin dalam larutan air.
Ultraviolet and Visible Spectroscopy

Although we see sunlight (or white

light) as uniform or homogeneous in
color, it is actually composed of a
broad range of radiation wavelengths
in the ultraviolet (UV), visible and
infrared (IR) portions of the spectrum.