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Air

Fungsi
1. Pelarut universal (salt, vitamins, sugar, gases, pigment)
2. Penunjang struktur bahan pangan
3. Air bahan pangan (menentukan kestabilan dan mutu
bahan pangan)
4. Menentukan padatan dari bahan pangan
5. Menentukan rendemen proses pengolahan
6. Reaksi kimia (reaksi hidrolisa)
Air dalam Bahan Pangan
1. Sebagai pelarut komponen-komponen kristal (gula,
asam, garam, dsb) sebagai medium dispersi
makromolekul hidrofobik (protein, gum dls)
2. Terserap pada lapis tipis pada permukaan
makromolekul (akibat dari ikatan hidrogen/van der
walls)
3. Terikat secara kimia dalam bentuk hidrat yang
stabil (monohidrat dekstrosa, protein dll)
KINDS OF WATER - DEGREE OF WATER BINDNESS

Monolayer Water is bound in food - restricted in its movement


due to charges, hydrogen bond, physical entrapment. Hard to
remove from food. Never be able to remove water completely.

Multilayer Water - additional layer of water around food


particle. Not as hard to remove as the monolayer.

Mobile or Free Water - consisted with ideal solution.


REACTION RATES IN FOOD AS A FUNCTION OF
WATER ACTIVITY
Moisture analysis
Why do we need moisture analysis ?

Material balance
Meeting the standards of product
Product stability (prevent deterioration, mold,
bacteria, insect damage)
Economic importance (H2O is cheap)
CONSIDERATIONS IN SELECTING THE
METHODS OF WATER ANALYSIS

Form of water present (free vs. bound water)


Example: % water in milk vs. non-fat dried milk
Nature of product :
Volatile compounds
Heat stable - loss of some food compounds
Unsaturated fat - oxidation - weight
How fast you can analyze sample
Accuracy and reproducibility
Availability and cost of equipment
Metode Analisis Kadar Air

Metode langsung
Oven: Oven udara, Oven vakum
Desikasi kimia
Kimia: Titrasi Karl Fischer, distilasi
Metode ekstraksi: GC, refraktometer
Metode tidak langsung
Metode listrik-elektronika: konduktivitas AC-DC,
kapasitas dielektrik, penyerapan pendek
Metode sonik/ultrasonik
Metode spektroskopi: IR, NMR
Water Determination Methods

Gravimetric: Oven method


Distillation method
Chemical methods: Karl Fisher method
Physical techniques: Infra red, gas
chromatography, NMR
As a general rule in all analyses, choose the
fastest simple convenient method which will
give results within the desired range of
accuracy - savings on time, labor costs, will
quickly cover capital expenditure.
Metode-metode penetapan kadar air
Tekanan Berat Waktu
Metode Suhu (oC) Jenis Sampel
(mm Hg) (g) (jam)
Pengeringan
135 760 2 2 Berbagai jenis pangan
oven
130 760 2-5 1-2 Keju, terigu,
125 760 2 4 Berbagai jenis
115 760 2 8 Berbagai jenis
105 760 2-10 16-18 Daging
Sampel
100-102 760 2-6 Tepung, ciklat/mentaga
tetap
Oven Vakum 125 100 5 5 Lemak/minuak
100 100 1-3 4-5 Susu bubuk, keju, produk daging
98-100 25 2-5 5 Kopi, tech, terigu
60-70 50-100 2-5 2-6 Buah kering, madu, sirup
Distilasi
85 760 10 0.5-1 Keju, produk daging, kopi
toluene
Desikasi kimia Sampel
25-30 10 2-5 Teh, rempah, rempah
tetap
Karl Fischer - - - - Teh, rempah, rempah
Metode Destilasi
Destilasi langsung (pertama kali)
Destilasi azeotropik
Metode Distilasi langsung
Alat Brown Duvel
Air diuapkan dari cairan yang
imisibel (immiscible) dengan
titik didih tinggi.
Sampel dipanaskan, dan air
yang menguap dikondensasi,
lalu ditampung dalam gelas
ukur dan ditentukan
volumenya.
Volume air yang tertampung
digunakan untuk menghitung
kadar air.
Metode Destilasi Azeotropik
Azeotropik: Air secara simultan dapat didistilasi dengan
cairan yang imisibel, pada suatu perbandingan yang tetap.
Contoh: Td air: 100oC, Td toluene: 110oC, Td air +
toluene (50:50): 85oC.
Titik didih air + cairan imisible menurun, sehingga dapat
diuapkan kondensasi air dan toluene terpisah
volume air diukur
Pelarut imisible:
Toluene (Td=110oC, =0.866 g/ml)
O-metil benzene (Td=144oC, =0.861 g/ml)
Tetra-kloretilen (Td=146.3oC, =1.6 g/ml
Metode Destilasi Azeotropik

Solvent Toluene
Condenser
Cold water xx
xxxxx Refluxing & water
xx Cold separation method
x x Graduated Trap
x
x
x

xxX x x
x
X x
x
x
x
x x
x
Samples & Solvent
Heating Mantle
Prosedur penetapan
Ke dalam labu erlenmeyer 300 ml
dimasukkan sampel yang kira-kira akan
memberikan antara 2-5 ml air. Untuk
mencegah percikan, ditambahkan batu
Cold water Cold x xxx didih.
xxx
xx
x
x
Toluene sekitar 75 ml ditambahkan ke
x
x dalam Erlenmeyer sampel
xxX xx
x
Alat-alat gelas yang diperlukan untuk
X xx
x x xx
x merakit alat destilasi dipasang seperti
pada Gambar.
Erlenmeyer dipanaskan sampai isinya
mendidih dan biarkan destilasi
berlangsung dengan kecepatan
kondensasi sekitar 2-4 tetes kondensat
per detik.
Prosedur penetapan

Destilasi dilakukan sampai tidak ada air


lagi yang terkondensasi.
Konsenser dibilas dengan toluene untuk
Cold water Cold x xxx
xxx
xx
membilas air yang mungkin masih
x
x menempel di bagian dalam kondenser.
x
x
Pemanas dimatikan dan tabung
xxX xx
X xx
x dibiarkan beberapa saat pada suhu
x x xx
x ruang
Air yang tertampung dalam gelas
penampung dibaca volumenya.
Kadar air ditetapkan dalam persen
terhadap berat awal
Keuntungan Metode Destilasi
Kadar air ditetapkan secara langsung dan hasil akhirnya
merupakan nilai kadar air yang nyata dan bukan karena
kehilangan berat sampel
Hasilnya sering lebih teliti dibandingkan dengan pada
penetapan dengan pengeringan oven, karena jumlah
sampel yang digunakan jauh lebih banyak, sehingga
penarikan sampel dapat lebih mewakili secara acak,
Waktu penetapan relatif singkat 0.5-1 1 jam
Peralatannya sederhana
Pengaruh kelembaban lingkungan dapat dikurangi
Dapat mencegah terjadinya reaksi oksidasi selama
pemanasan
Cara mengerjakannya sederhana dan mudah ditangani.
Kekurangan Metode Destilasi
Bagian permukaan dalam peralatan gelas harus dalam
keadaan sangat bersih sehingga air tidak menempel
padanya
Sebagian senyawa seperti gliserol dan alkohol mungkin
terdestilasi bersama-sama air yang dapat menyebabkan
data kadar air yang didapat menjadi lebih tinggi
Pelarut-pelarut yang digunakan seperti misalnya toluene
mudah terbakar
Sebagian pelarut mungkin beracun, misalnya benzene
Ketelitian membaca volume air yang terkondensasi
terbatas apalagi jika tabung penampungnya sempit,
sehingga ada sebagian pelarut yang mungkin terperangkap
di sana dan menimbulkan kesalahan pembacaan kadar air.
Chemical methods

Karl Fisher Method: Standard technique for low moisture


foods, such as dried fruit, vegetable, candies, chocolate,
roasted coffee, oils and fats
Good for reducing sugars and protein-rich foods and good for
foods with high volatile oils.
The reduction of iodine by SO2 in the presence of water

Theory: 2 H2O + SO2 + I2 H2SO4 + 2HI


Principle of Karl Fischer Titration

Modified to include methanol and pyridine to dissolve iodine


and SO2:

C5H5N.I2 + C5H5N.SO2 + C5H5N + H2O 2C5H5N.HI + C5H5N.SO3

C5H5N.SO3 + CH3OH C5H5N(H)SO4.CH3

It means: For each mol of water, 1 mol of I2, 1 mol of SO2


and 3 mol of pyridine, 1 mol of methanol are required
Karl Fisher Method

1. + + + H2 O 2 +
N N N N N
I2 SO2 HI SO3

2. + CH3 OH
N N
SO3 H SO4 CH3
Brown Mahogany Color
Karl Fisher Method
Water is extracted by absolute
methanol and titrated by Karl Fischer
Reagent
Karl Fisher Reagent (KFR): Dissolve the
Iodine, SO2 and Pyridine in methanol
(1: 3 : 10).
This mixture is unstable storage
separately: I2 in methanol, SO2 in
pyridine mix shortly when used
KFR is very sensitive to water
titration in a closed system
dilengkapi pengering udara (silica gel)
Standardization of KFR
Before the amount of water found in a food
sample is determined, a KFR water equivalent
(KFReq)must be determined represent the
equivalent amount of moisture that reacts
with 1 ml of KFR.
Use tartrate dihydrate (Na2C4H4O6.2H2O) as
standard (containing 15.66% water and very
stable)
Standardization of KFR
KFReq (mg H2O/ml) =

36 g H2O/mol tartrate x S x 1000


230.08 g/mol x A

where: S = weight of tartrate dihydrate


A= ml of KFR required for titration

Once the KFReq is known, the MC of sample can be


determined:

% H2O = KFReq x Ks x 100


S
where:
Ks = ml of KFR used to titrate sample
S = weight of sampel (mg)
Physical Techniques of
Water Determination

Gas Chromatography
Infrared Spectrophotometry
Nuclear Magnetic Resonance
(NMR)
Infrared spectroscopy
Measurement of the absorption of different
frequencies of IR radiation by foods.
IR radiation is electromagnetic energy with
wavelengths longer than visible light but
shorter than microwaves (0.8-100m).
A molecule can absorb IR radiation if it
vibrates in such a way charge distribution and
its electric dipole moment changes during the
vibration.
Spektrum Elektromagnetik

Radiasi
elektromagnetik
mempunyai sifat:
gelombang
elektromagnetik
berkas partikel
atau foton

m = 10 -10 m m = 10-6
nm
m = 10 -9 m cm = 10-2
Near-infrared absorption bands of
various food constituents

Constituents Absorber Wavelength (m)


Water -OH 1.92-1.95
Protein -NH 2.08-2.20
1.56-1.67
Lipid -CH2 1.68-1.76
Carbohydrate C-O, O-H 2.06-2.15
Infrared Spectroscopy
Water exhibits a number of
absorption bands in the
near infrared (IR) region of
the spectrum. 2.0

.
Based on measuring the 1.5
absorption of OH groups. X

Bands at 0.97-1.95 m are 1.0


X
widely used. 0.5 X

For fruit, vegetable, flours.


The sensitivity is 1 ppm 0 20 40 60 80 100

The moisture content is % Moisture by Oven Method

determined by using a
calibration curve
Infrared Method

Direct method:
The ratio of reflected intensities of the 1.93 m
and 1.45 m bands is used as a measure of
water content.
Indirect method:
Water is extracted from a food by
dimethylsulfoxide (DMSO), dimethylformamide
or methanol before IR measurements are taken.
Gas chromatography
Based on extracting the moisture with an organic
solvent and determining water in the extract by gas
chromatography.
Sample is ground and blended in the presence of
absolute methanol. 2 l is tested in gas liquid
chromatography.
The peak area measurement is obtained and related
to a series of standards containing known amounts of
water in methanol.
For variety of foods, such as cereal products, fruits
and fruit products (MC 8-65%).
Moisture content of fruits and fruit products
as determined by Vacuum oven and Gas
Liquid Chromatography (GLC)
Product Averg moisture(%)
Vacuum oven GLC
Guava 87.30 87.01
Papaya 87.19 86.60
Fresh banana 69.66 70.33
Air-dried banana 4.23 4.13
Freeze-dried banana 4.29 4.51
Raisin 15.46 16.94
Nuclear Magnetic Resonance (NMR)
Technique

The H atoms in water have nuclei which possess magnetic


properties. They behave as small bar magnets, creating their
own magnetic fields.
If placed in an external magnetic field, the axes of these
nuclei tend to become oriented in a specific, fixed direction
with regard to the applied field.
H nuclei of water will vibrate (spin-orientation) in a fixed
magnetic field and proper radio frequency.
The amount of energy absorbed during this process is related
to the number of H nuclei in the magnetic field.
Nuclear Magnetic Resonance (NMR)
Technique

NMR measure the H nuclei, which is related to the


amount of water
For foods with limited amounts of soluble solids as the H
nuclei of the solutes absorbed energy in NMR
spectrophotometer.
Advantages: Rapid (1 minute), Non-destructive, Sensitive
and Accurate.
Disadvantages: expensive cost of operating and
maintaining the NMR instrument, need to obtain precise
calibration curves
The technique has been applied to determine bound and
free water. Based on these, there are two methods:
freezing method and room temperature method
Nuclear Magnetic Resonance Spectrometer

Sample

R-F Detector
Transmitter
0 20 40 60 80 100

% Moisture by Oven Method


Transmitter Coil Receiver Coil
COMPOUNDS

H O H
CH3 O H

CH 3CH2 O H
Nuclear Magnetic Spectrum
Nuclear Magnetic Resonance (NMR)
technique

Freezing method:
NMR distinguishes between frozen (free) and
unfrozen (bound) water at a temp < 0oC.
NMR distinguishes between ice and water
because the signal exhibited by ice is much
broader than that of unfrozen water.
This signal can be perceived by signal
amplitude differences at specific frequencies.
Nuclear Magnetic Resonance (NMR)
technique

Room temperature techniques:


Bound water is its specific molecular mobility
at room temperature (it exhibits a broader
signal than free water).
This difference in signal can be measured.
Enable determine bound water content of
wheat flour, corn starch, and egg white at
room temp without prior freezing (Sudhakar
et al., 1979).