CHAPTER 5

REFRACTIVE INDEX BASED FOCS

Chapter 5/R.I. Based FOCS 127

5.1.Introduction:
Refractive index is an important characteristic of optical material.
Simple and high-precision method of measuring refractivity of liquid has been
required for the material analysis and also for applications like environmental
pollution monitoring of both river and sea water[5.1].
Precise measurement of refractive index of transparent liquids is vital
to design of optical instruments and is also of great value in chemical work.
The knowledge of refractive index of a substance is useful in identifying and
determining the concentration of organic substances.
Practically the measurement of index of refraction of solid samples is
done by precise angle measurement. The refractive index of liquid samples
can be measured in this way with the use of hallow prism[5.2]. Other
techniques based on the critical angle effect are generally more accurate
[5.3]. Abbe refractometer based on this principle is widely used [5.2,5.4]. In
general an Abbe refractometer is used to measure the refractivity of
liquids[5.5]. Implementation of total internal reflection and prism coupling are
widely used techniques but the experimental arrangements are complex and
more sensitive to external perturbation. H. Hattori et al [5.6] describe a new
method for measuring the refractive indices of liquids. This method uses the
minimum deviation of laser beam in a cylindrical cell that contains the liquid
sample. The principle is nearly same as that of generation of natural rainbow.
This method was used to detect the refractive index over a range from 1.30 to
1.37. This range can cover the refractive indices of many liquids such
methanol, water and ethanol etc. It gives linear relationship between the
minimum deviation and refractive index.
Fiber Optic Sensors (FOS) have received considerable attention in the
recent years because of their inherent immunity to electromagnetic
interference, safety in hazardous or explosive environment, high sensitivity,
and long distance remote measurements. The miniature size, low cost,
intrinsic safety and ease of installation of FOS makes this system ideal for the
applications in various engineering areas including numerous in-line chemical,
food, beverage, or medical analysis and monitoring operations. Due to this,
fiber optic sensing technique is used to develop refractometer.

Chapter 5/R.I. Based FOCS 128

5.2 Rl measurement by other FOS:
Various fiber optic sensing techniques were used to develop
refractometers. Takeo and Hattori [5.7] proposed refractometer by measuring
attenuation of light guided by optical fiber within the liquid. Fibers with
selectively etched cladding and small bending radius have proved as good
configuration for measurement of refractive index of liquids. They also applied
the refractometer thus built to monitor the skin dehydration [5.8]. M.
Laguease [5.9] presented an optical fiber refractometer for liquids, which
eliminates the influence of attenuation due to the liquids. In this method two
pairs of fibers placed face to face on the same axis and separated by two
different distance were used. Assech et al [5.10] proposed a fiber Bragg
grating refractometer using evanescent field refractive index fiber sensor that
compromises a 42mm Bragg grating in an etch fiber. However, none of them
can be used with for long term monitoring. Recently Yu-Lung Lo et al [5.11]
developed a stable optical fiber refractometer using path-matching differential
interferometries (PMDI) with two parallel Fabry-Perots sensing cavities. The
change of refractive index is obtained by mixture of de-ionized water and
ethanol with resolution of 10~5.
F. Meriaudeau et al [5.12] presented the gold island fiber optic sensor
for refractive index sensing based on gold island surface plasmon exciation.
Another technique is to use the tapered fiber for refractive index measurement
[5.13]. It has been shown that the sensitivity of sensor depends on NA of fiber,
the taper ratio and refractive index of absorbing medium. However, these
type sensor configurations involve careful and accurate etching of cladding. A
simple configuration uses the end-separated fibers where T-R coupling is
decided by medium filled in the gap [5.14]. The configuration, however, is
difficult to handle because of precision needed in aligning the two fibers. The
fiber has to be placed exactly opposite to each other to get maximum
sensitivity.
A fiber optic probe is used for refractive index measurement, in which
process fluid is allowed to flow into a miniature cavity on the probe which acts
as a dual reflective surface or mirror, which changes the spectral refractive

Chapter 5/R. I. Based FOCS 129

characteristics of light source to the refractive index of the process fluid[5.15].
The advantage of these temperature compensated probe is that a single
T. Takeo and H. Hattori report a fiber optic refractive index sensor
which consist of silica glass fiber bent into U shape with bending radius of
typically several hundred micrometers. The cladding at the tip of sensor is
stripped off. The sensing mechanism is based on variation of output intensity
that is induced by radiation loss at bend , which enable us to measure
refractive index of outer medium. A typical resolution for refractive index
measurement was measured to be the third decimal point. [5.16]
Other techniques include a planar laser-induced fluorescence
technique[5,17], an invasive heat marker method[5.18], interferometric
techniques[5.19-5.21], and a phase-locked-loop ultrasonic method[5.22].
Refractometers are used routinely to evaluate the refractive index to
determine the concentration of liquid mixture[5.23].
In this work it is proposed to use a two-fiber probe and reflector based
on the reflective intensity modulation. The liquid under test fills the gap
between probe and reflector. Depending upon the refractive index of liquid,
angle of emittance will change which, will decide the received output power by
receiving fiber. In this sensor the measurand is used to induce modulation of
light reflected from reflecting surface. For the multi wavelength study a novel
probe is developed which consists of outer ring of illuminating fibers and
center read fiber. Various configurations of FOS based on the principle of
reflective intensity modulation are earliest to become commercial and
practical because of their effective cost performance. The next section
describe the developed extrinsic FOS for the measurement of refractive index
of liquids based on the reflective intensity modulation.

5.3 Measurement Principle:

The FOS discussed here is extrinsic type. So the light is carried up to
the modulating zone by illuminating fiber (T-fiber) where the properties of the
incident light are modulated by modulator. The modulated light is carried out
to the detector by read fiber (R-fiber). The modulating zone is a reflector kept
at distance x from transmitter and liquid is used as medium.

Chapter 5/R.I. Based FOCS 130

 T-Fihe
ter R-Fiber T-Fibe R-Fiher

._ iqui iquid (ni),

\^\\\\\x\vV\\\\~
Reflector

\4—T-Fiber Image T-Fiber Image

(a) (b)

Figure 5.1 Fiber Optic Sensor arrangement for refractive index measurement

As shown in figure 5.1 the incident light in the form of cone of emittance from
illuminating fiber gets reflected back in the form of expanding cone of light towards
the receiving fiber. The cone of emittance depends upon the refractive index of liquid.
As shown in figure 5.1(a) the liquid having the refractive index ni filled between the
gap in probe and reflector. As described in chapter 3 the angle of emittance is 9 i is
given by equation
9 i =sin" 1 (NA/n 1 ) (5.1)
and radius of reflected cone qi is given by equation,
qi=a + (2x + h)tan(0i) (5.2)
The output power may be determined by considering the overlap area and
cross-section of reflected cone emitted by the image of emitting fiber [5.24].
The receiver collects the optical power that falls in its cone of acceptance and
guides it up to the detector. This is estimated by cross section of cone of
emittance of image fiber and core area of the receiver fiber. Now the gap is
filled with liquid having the refractive index n 2 as shown in figure 5.1(b). Since
n2 > n^ the angle of emittance is 0 2 < 61 so q 2 < qi hence the overlapping
area decreases. Thus the received output power decreases. Hence for certain

Chapter 5/R.I. Based FOCS 131

value of the fiber tip-reflector gap(x), the received power depends upon the
refractive index of liquid.

5.4 Rl measurement on Organic solvents:

Experimentation is carried out using available organic solvents like
methanol, pentanol, etc. Test bench, as explained in chapter 4 is used for
measurements.. The Multi-wavelength probe is used for studying the effect of
wavelength variation on refractive index of transparent liquids
As disused in previous chapter, the sensitivity of sensor depends upon
the distance between reflector and mirror, so initial experiments are carried
out by changing this distance. In this case distance between the probe and
mirror is varied using stepper motor controlled by PC, Inputs and outputs are
change using the data acquisition card AX-5412 HG which is controlled
through PC
The initial experiment is carried out by varying the distance between
probe and reflector for air medium between them. . The figure 5.2 shows a
plot of power collected versus probe separation from reflector. The blind
region, linear and no-linear regions of the FOS behavior are clearly
observable.

> 0.6 T
I 0.5
•D 0.3
£ 0.2
E 0.1
o 0I
0 1 2 3 4 5 6 7 8 9 10
x (mm)

Figure 5.2 FOS response for air medium

Chapter 5/R.I. Based FOCS 132

 As the distance increases beyond the blind region limit, the reflected
cone overlaps the receiving fiber core and hence the output intensity
increases. This relation is continued until the entire face of receiving fiber is
illuminated with reflected light. After the optical peak curves follows the
expected parabolic function. This in agreement with the experimental results
of Daniel Sagrario et al[5.25] and simulation results reported in chapter 3.
The same experiments are carried with water as a medium between
probe and reflector. The results obtained are shown in figure 5.3. From the
equation (5.1) as the refractive index of the support medium increases, angle
of emittance decreases so that radius of reflected cone decreases for the
probe-reflection separation(x) and output power collected also decreases.
After the blind region is crossed, output is expected to be more than which is
obtained for air medium because of increase in power density. Indeed
the observed results match with expected results as seen from figure 5.3.

^ 0.7 r
g. 0.6
D 0.5
4
£ °"
85 0-3
75 0.2
E 0.1
o 0 i
z
0 1 2 3 4 5 6 7 8 9 10
x (mm)
Figure 5.3 FOS response for air & water medium

Chapter 5/R. I. Based FOCS 133

 Encouraged with these results it was decided to repeat the
experiments with different fluids of higher refractive indices. The liquids
used were Methanol(ri=1.329), Pentanol-1(ri=1.410),1-Hexanol(ri.=1.418),
and 1-Decanol (ri=1.437). The results obtained are illustrated in figure 5.4. As
refractive index increases, angle of emittance decrease hence received output
decreases because of less overlapping area for smaller x<4.0 mm. But after
this distance density of reflected light increase so output intensity increases.
As shown in figure, sensor produces higher output for increase in refractive
index at about x=6mm.

1
I
t 0.8
° 0.6
a>
£ 0.4
re
re
E 0.2
o
z
oi
0 1 2 3 4 5 6 7 8 9 10
x (mm)
Figure 5.4 FOS response for refractive index
variation

The experiments are repeated with different LEDs with the help of
designed probe in conjunction with PC based test bench.. It was found that
sensor distinguishes liquids of different refractive index for the separation
>6mm.
From the principle of operation and the simulation results of figure 3.8,
it was expected that output intensity increases linearly as function of
refractive index of medium. The experimental observations with reflector-
probe gap of 6mm are plotted against the refractive index of liquid as shown
in figure 5.5(a). From the simulation results of figure 3.8, those corresponding

Chapter 5/R. I. Based FOCS 134

to refractive index range of the specimen used, are reproduced in figure
5.5(b) for comparison.

1
0.9 _ /•
+•>

o
+•>
3
0.8
0.7
-— RED
• GREEN
y
a 0.6 + BLUE
*->
3 0.5
O
•D
a) 0.4
N
0.3
E
0.2
0.1 ^ ' ^

0 I el

1.11 1.22 1.33 1.44

Refractive index of liquids

Figure 5.5(a) Response of FO sensor for RED, GREEN

and GREEN LED

2.50E-02

* 5.00E-03

0.00E+00
1 1.11 1.22 1.33 1.44
Refractive index of medium

Figure 5.5(b) Simulated response of FO sensor at

x=6mm

Chapter 5/R. I. Based FOCS 135

 The striking similarity of the nature of variations testifies the usefulness
of simulations as well as the validity of experimental data. The sensors also
shows the dependence of the output on color(wavelength) of source as seen
from the plots for RED, BLUE and GREEN LEDs.
From the results presented through the figures 5.3-5.5 it is seen that
the multi wavelength probe designed for refractive index measurement bears
a good promise. Appropriate mechanical probe design and circuit packaging
will produce a handy instrument suitable for many applications.
In this section the dependence of FO sensor output on refractive index
of medium has been demonstrated. This is in agreement with simulation
results suggesting the utility of the developed probe for detecting changes in
refractive index of the medium. Apart from pure solvents which have different
refractive indices, there are mixtures of various types which also alter the
refractive index of a given medium. Following sections demonstrate the use of
developed probe for such mixtures.

5.5 Alcohol and water mixture measurement:

5.5.1 Introduction:
Methanol (CH3OH) is the simplest alcohol, containing one carbon
atom. It is a colorless, tasteless liquid with a very faint odor and is commonly
known as "wood alcohol." Methanol is used in a number of consumer
products, including paint strippers, duplicator fluid, model airplane fuel, and
dry gas. Most windshield washer fluids are 50 percent methanol[5.26]

Methanol's physical and chemical characteristics result in several

inherent advantages as an automotive fuel. Some methanol benefits include
low emissions, high-performance, and less flammable than gasoline[5.27].

The commercialization of methanol-powered fuel cells will offer

practical, affordable, long-range electrically-powered vehicles with zero or
near-zero emissions while retaining the convenience of a liquid fuel. By 2004
or sooner, fuel cells operating on methanol will power a variety of cars and
buses in the United States and worldwide[5.28].

Chapter 5/R. I. Based FOCS 136

 Chemical Properties: As engine fuels, ethanol and methanol have
similar chemical and physical characteristics. Methanol is methane with one
hydrogen molecule replaced by a hydroxyl radical (OH)[5.29].

Ethylene glycol is a clear, colorless, odorless, viscous liquid with a

sweet taste, that can produce dramatic toxicity. It is commonly found in homes
and industry. It is found most commonly in antifreeze, automotive cooling
systems, and hydraulic brake fluids. In an industrial setting it is used as a
solvent or as the raw material for a variety of processes[5.30]. Many cases of
ethylene glycol poisoning results from accidental ingestion by children who
can take in large amounts since the substance tastes good. Alcoholics may
also ingest this substance as an ethanol substitute.

Considering the important uses of these alcohols, it is necessary to

detect the concentrations of these alcohols in mixture with water. The
developed sensor is used to detect the concentration.

5.5.2 Experimentation:
Different concentration methanol solutions were prepared by mixing
pure methanol with distilled water. Range of concentration is from 0-100%.
The developed sensor was used to detect the concentration of methanol in
mixture.
Ethylene glycol is not easily soluble in water. So magnetic stirring was
done to get homogenous mixture. Magnetic stirring was carried out for 5
minutes at room temperature. Rest of the procedure is same as explained
above.

5.5.3 Results and discussion:

The response of developed sensor for methanol water mixture with
different colored LED illuminations is shown in figures 5.6(a) and figure
5.6(b).

Chapter 5/R. I. Based FOCS 137

 20 40 60 80 100
Concentration of Methanol(%)

Figure 5.6(a) Response of FO sensor for Methanol-Water

mixture for RED LED

1.25
20 40 60 80 100
Concentration of Methanol(%)

Figure 5.6(b) Response of FO sensor for Methanol-Water

mixture for BLUE LED

Chapter 5/R. I. Based FOCS 138

 It is seen that as methanol concentration in water increases the sensor
output initially increases, goes through maxima and reduces again. Literature
survey revealed that indeed such behavior of refractive index variation is
reported. Figure 5.7 shows the experimental observation obtained by Jon P.
Longtin and Ching-Hua Fan[5.31] along with the standard data obtained from

1.343 -

O
o
T J^~"~"" "

O #
CM
/k * \ * ^
"55 1 . 3 4 0 - X = 589 nm / • d. N.
£ • A
ixtu

^4/ (
" \
2 s • A \

*» 1.335 -
»»-
X
o
•
V X " 632.8 nm
" A \
8 •
A \
?
— i>
4)
J
> 1.330 i
A \
t> terature values [5.31]
efra

L
• 0-60% methanol
DC A 0-60% water i

1.325 - r - •• • I •" i "

1
20 40 60 80 100
Concentration of Methanol (mass%)

Figure 5.7 Methanol-water mixture refractive index measurement

CRC Handbook[5.32]. Longtin and Fan have carried out the measurement
with the help of a Laser based refractive index measurement system with a
UDT SL5-2 linear position sensor and PC based system to precisely monitor
the beam deflection through cuvette. The similarities between the nature of
curves from figure 5.6 and 5.7 are clearly observable. The deviations of the
observed sensor output voltages from the trend curves in figure 5.6 can be
attributed to the experimental approximations in preparing the mixtures.
However, the purpose of demonstrating the usability of developed sensor is
served. Figure 5.6 also shows the color depend ace of the variation.
Figure 5.8 shows the results obtained for the ethylene glycol-water
mixture. There is a almost linear rise in the sensor output predicting a linear
change in the refractive index of mixture as the ethylene glycol concentration

Chapter 5/R.I. Based FOCS 139

 4.5
4
3 5
T -
a «•
> *
• RED
£2.5
3 • GREEN
o 2 A BLUE
6 'L
^ 1.5

0.5 - l
0 -
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Concetration of Ethylene glycol(%)

Figure 5.8 Response of FO sensor for Ethylene glycol-Water

mixture

increases. Refractive indices of the same samples were measured using

standard Abbe's refractometer. Figure 5.9 shows the variation of refractive
index of the mixture with concentration. Similarity of the nature of two plots is
revealing. Figure 5.10 shows the sensor output voltages plotted against the
measured refractive index. Esteban et al[5.33] have used a surface plasmon
resonance based fiber optic sensor for the determination of refractive index of
ethylene glycol and obtained similar results. In their work they have also
referred to the Ph.D. thesis of R. Alonso[5.34] giving an empirical formula for
the refractive index variation of the ethylene glycol-water mixture with varying
concentration as

«(7>/; //2O (7') + 0.111^f- (5.3)

'tot

where n is refractive index of mixture, n„ 0 is the refractive index of

water, Velh is the volume of ethylene glycol, and Vtot is the total volume of
mixture.
This also suggests the linear variation, further supporting the results
shown in figure 5.8.

Chapter 5/R.I. Based FOCS 140

 X
<u
V
,>
o
TO

•o
2
3
V)
(0
V

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Concentration of Ethylene glycol(%)

Figure 5.9 Variation of refractive index for Ethylene glycol-

Water mixture.

1.323 1.329 1.335 1.341

Measured refractive index

Figure 5.10 Response of FO Sensor for variation in

refractive index

Chapter 5/R. I. Based FOCS 141

5.6 Measurement of salinity of water:
5.6.1 Introduction:
Water is an amazing solvent. It is able to retain large amounts of salts
and other materials in solution. When this occurs, the salts change the
properties of water[5.35]. Similarly the salts-water mixture shows changes in
refractive index. Seawater has a higher density than fresh water. Sea water
contains many dissolved substances and these add mass to water within
which they are dissolved, thereby producing a greater mass per unit volume,
or density, higher than that of pure water. The amount of salts dissolved in
water is called salinity. Salinity is measured in g per 1000 ml i.e. grams per
liter and a special symbol is used: o/oo by weight. A standard value for the
salinity of sea water is 35 %o[5.36].
Salinity is an important unitless property of industrial and natural
waters. It was originally conceived as a measure of the mass of dissolved
salts in a given mass of solution. The experimental determination of the salt
content by drying and weighing presents some difficulties due to the loss of
some components. The only reliable way to determine the true or absolute
salinity of a natural water is to make a complete chemical analysis. However,
this method is time-consuming and cannot yield the precision necessary for
accurate work. Thus, to determine salinity, one normally uses indirect
methods involving the measurement of a physical property such as
conductivity, density, sound speed, or refractive index. From an empirical
relationship of salinity and the physical property determined for a standard
solution it is possible to calculate salinity. The resultant salinity is no more
accurate than the empirical relationship. The precision of the measurement of
a physical property will determine the precision in salinity.
There are two main methods of determining the salt content of water:
Total Dissolved Salts (or Solids) and Electrical Conductivity. The Total
Dissolved Salts(TDS) is measured by evaporating a known volume of water to
dryness, then weighing the solids residue remaining. Electrical
conductivity(EC) is measured by passing an electric current between two
metal electrodes in a water sample and measuring how readily current
flows(be conducted) between the electrodes. The more dissolved salts in

142
water, the stronger the current flow and higher the EC. Measurements of EC
can be used to give an estimate of TDS. The EC can effectively converted to
TDS by following relationship^.37]
TDS(mg/L)=EC(|aS/cm at 25°) * 0.6
Bergman[5.38,5.39] developed fiber optic probe to measure salinity in
liquids. A fiber optic sensor based on surface plasmon resonance for the
determination of the refractive index is used for measuring degree of salinity
of water[5.33]. A new type fiber optic Bragg grating sensor based on
hydrogels is used for measuring the salinity[5.40]. The sensing mechanism in
this device is based on mechanical stress that is induced in the chemically
sensitive water swellable(hydrogels) coating when the water escape from it.
The stress in the hydrogels coating stretches and shifts the Bragg wavelength
of the fiber Bragg grating.

5.6.2 Experimentation:

The experiments were carried out with dilute pure NaCI solutions.
NaCI solutions of different molarities from 0-1 Molar concentration were
prepared by dissolving measured weights of NaCI salt in distilled water.
Electrical conductivity of each of the specimen was the measured using
standard conductivity meter. The values are tabulated in table 5.1. the
developed sensor output voltages with 5 mm reflector-probe spacing were
then noted as a function of concentration.

Table 5.1
NaCI Concentration Electrical Conductivity
(Molarity) (mmho-cm)
0 0.72
0.1 9.02
0.3 17.07
0.4 24.8
0.4 30.7
0.5 36.6

Chapter 5/RI Based FOCS 143

5.6.3 Results and Discussion:
Figure 5.11 shows the NaCI concentration response of the developed
sensor. The out of sensor increase with increase in concentration.

0.1 0.2 0.3 0.4 0.5

Nad concentration(Molar)

Figure 5.11 Response FO sensor for NaCI concentration

The conductivity of same solutions was measured with standard

conductivity meter. Figure 5.12 shows variation of output for change in
electrical conductivity. The sensor output also increase with increase in
conductivity. The conductivity in this case represents a measure of dissolved
ion concentration or effectively the salinity.

3.8 -i

3.7

35
~. 3.6

I
J2

S- 3.4
3
0
5 3.3

1 3.2
3.1

3
() 10 20 30 40

Measured Conductivity(m mho-cm J

_

Figure 5.12 FO sensor output as a function of conductivity

Chapter 5/RI Based FOCS 144

J. Cong et al{5.40] have carried out salinity measurements in dilute NaCI
solutions using fiber optic Bragg grating(FBG) sensor. The FBG sensor
essentially based on swelling of hyhrogel when immersed in water and
release of some water due to shrinkage in NaCI solution resulting in Bragg
wavelengths suffering blue shift. They have studied the change in blue shift
as a function of NaCI concentration in the range of 0-0.7 mol/lit. It was
observed that the sensitivity of FBG sensor drops when it is exposed to NaCI
solutions with concentration higher than 0.5-0.7 mol/lit. A comparison of the
results obtained using the developed in present work with those of Cong et al
made. Figure 5.13 shows the relationship between the observed output and
the observed shift reported by J. Cong et al based on their FBG sensor.
Correlation between the two is clearly seen. This substantiates the utility of
the developed sensor.

U.U

•
^^
« 3.4
o
>
"3 3.3 y*
Q.
+* »/• s
3
2 3.2
o
w
c

3 i i i i

0.01 0.02 0.03 0.04 0.05 0.06

Negative shift in Bragg
wave le ngth( nm)[5.39]

Figure 5.13 FO sensor output for shift in Bragg

wavelength

Chapter 5/RI Based FOCS 145

5.7 Brix measurements(Brix Refractometer):
5.7.1 Introduction:
Brix scale is generally used as a measure of percentage of dissolved
solids(as sucrose) in fruits, juices and soft drinks. Refractometric Brix
measurements are common in such industries for the Brix of such
specimen[5.41]. Refractometers are simple optical instruments for
measuring the dissolved solid content of fruits, grasses, and vegetables
during all stages of growth. The solids that are dissolved in the juice of
plant tissues will bend light rays in proportion to the quantity of all
the atoms, the atomic weight of the elements, and the number of the
covalent bonds in the combination of atoms such as sugars.
Refractometer has also been used extensively in the grape and citrus fruit
industries[5.42]. Refractometers measure in % sucrose by weight (Brix0)
and can be calibrated with distilled water and/or with sugar standard
solution.
In the present work refractive index based FO sensor has been
developed. An attempt has been made to use the same sensor for
measurement of Brix in molasses. Experimental studies on Brix measurement
in molasses have been carried out using the developed sensor. Following
section gives the brief definitions and terminologies associated with Brix
measurement in brief followed by the details of experimentation and results
obtained.

5.7.2 Definitions and terminologies:

Molasses is output as a by-product in the last stream of the sugar
refining. Initially the term molasses referred specifically as the final effluent
obtained in the preparation of sucrose by repeated evaporation, crystallization
and centrifugation of juices from sugar cane and from beets. Today, several
types of molasses are recognized and in general any liquid feed ingredient
that contains in excess of 43% sugar is termed as molasses [5.43].
Molasses contains about 20% water and 80% solids, out of which total
sugars are to be extent of 50 to 55% and non-sugars are to be the extent of
25 to 30%. The total sugars may consists of about 48% sucrose and reducing

Chapter 5/RI Based FOCS 146

sugars and 2% raffinose. The total sugars content of molasses is mainly
responsible for its use as raw material in fermentation industries to produce
many chemicals like ethyl alcohol, yeast, monosodium glutamate, lysine, citric
acid, lactic acid, oxalic acid etc[5.44].
One important measurement of molasses is Brix. Named after the
Austrian scientist Adolf Brix. The Brix scale is used solely for pure sucrose
solutions and graduated so that its readings at a specific temperature
represent the percentage of sucrose, by weight, in a solution. In addition to
sucrose, molasses contains other sugars such as glucose and fructose, so
the Brix scale is not completely reliable for measurement of total sugars in
molasses. In the molasses community, therefore, Brix is representative of
specific gravity. In the United States, for instance, the standard Brix of
molasses following dilution is 79.5°F. Prior to dilution, the Brix of molasses is
typically 90° F. This product, called high-Brix molasses, is much too thick to
use in livestock feeds. Viscosity is also important to molasses producers and
feed manufacturers. Simply put, viscosity is the measure of resistance to flow,
its thickness or thinness. Numerous factors may affect the viscosity of
molasses. Characteristics of the sugarcane, such as its variety or maturity,
may affect viscosity, as may peculiarities in processing and environmental
temperature. In general, viscosity is reduced by heat and increased by cold.
The Brix scale or % solids (as sucrose) are well known and utilized in the food
and chemical industries to measure dissolved solids-primarily sugar-in fruits,
juices and soft drinks. Additional applications include determining fruit
ripeness by checking dissolved sugar level.
The Association of American Feed Control Officials(AAFCO,1982)
describes the following types of molasses[5.43].
1. Cane Molasses: is a by-product of the manufacture or refining of
sucrose from sugar cane. It must contain not less than 46 % total
sugars expressed as invert. If its moisture content exceeds 27 %, its
density determined by double dilution must be less than 79.5° Brix.
2. Beet Molasses: is a by-product of manufacture of sucrose from sugar
beets. It must contain not less than 48 % total sugars expressed as

Chapter 5/RI Based FOCS 147

 invert and its density determined by double dilution must be less than
79.5° Brix.
3. Citrus Molasses: is the partially dehydrated juices obtained from the
manufacture of dried citrus pulp. It must contain not less than 45 %
total sugars expressed as invert and its density determined by double
dilution must be less than 71.5° Brix.
4. Hemicellulose Extract: is a by-product of manufacture of pressed
wood. It is the concentrated soluble material obtained from the
treatment of wood at elevated temperature and pressure without use of
acids, alkalis, or salts. It contains pentose and hexose sugars, and has
a total carbohydrate content of not less than 55%.
5. Starch Molasses: is a by-product of dextrose manufacture from the
starch derived from corn or grain sorghums where the starch is
hydrolyzed by enzymes and/or acids. It must contain not less than 43%
reducing sugars expressed as dextrose and not less than 50% of total
sugars expressed as dextrose. It shall contain not less than 73% total
solids.
Table 5.2 represents an approximation of total solids content. Recent
production estimates for the various types of molasses show that of the total
United State supply, 60% was cane molasses, 32% was beet molasses, 7%
was starch molasses and 1% citrus molasses, starch molasses and
hemicellulose extract is quite limited[5.45].

Table 5.2
Item Cane Beet Citrus Extract Starch
Brix 79.5 79.5 71.5 65.0 78.0
Total Solids(%) 75.0 77.0 65.0 65.0 73.0
Specific Gravity 1.41 0.41 1.36 1.32 1.40
Total Sugars(%) 46.0 48.0 45.0 55.0 50.0

Chapter 5/RI Based FOCS 148

 Many value added products are already available from bagasse, which
is perhaps the major by-product of the cane sugar industry, in terms of bulk.
The other major by-product or co-product in cane manufacturing is molasses
and again many value added products are available through fermentation and
chemical transformations[5.44].
Molasses is used in large number of industries for the product of ethyl
alcohol, denatured spirits, absolute alcohol, rum, yeast, butanol, citric acid
etc[5.46]. The molasses trade commonly uses the term Brix as an indication
of specific gravity [5.47]. The Brix scale is the same as the Balling scale,
which is a measure of what the sugar content of a liquid would be if all the
dissolved and suspended solids were sugar. Expressed another way, it is the
sugar content of a sugar solution with the same specific gravity as the sample.
Thus, an 80° Brix molasses has a specific gravity of 1.416, which is the same
as a sugar solution containing 80% sugar by weight. Brix is measured using a
hydrometer originally intended only for sugar solutions. The world molasses
trade tends to center on New Orleans, Louisiana, even though the US
domestic molasses production is relatively low.
A hydrometer uses the principle- density to measure sugar
content[5.48]. Hydrometer readings are important during fermentation, and
most wine makers measure Brix at least once each day to monitor the speed
and consistence of their fermentation. Moderate drops in sugar each day
shows normal fermentation, and if an unusual change in the sugar is
observed, the wine maker can make corrections promptly [5.49].

5.7.3 Experimentation:
The experimentation was carried out in two stages.
1. Initial run to observe the feasibility
2. Calibration of the sensor output against the standard hydrometric
readings.
Initially the developed system is used to study the response of sensor
to the change in the concentration of molasses. The sample was prepared by
taking the 10-ml of pure molasses and diluted to 100 ml in distilled water to
get 10 % of molasses solution. The same procedure is repeated for obtaining

Chapter 5/RI Based FOCS 149

different concentration of molasses solution. The sample solution is placed in
cell and out put voltage is measured for different concentration of molasses
for different distance between probe and reflector.
The sensor response is then calibrated. The sample is prepared for
calibration by taking 80 ml of pure molasses and diluted to 262 ml using
distilled water. This solution should be free from air, suspended matters and
insoluble impurities. The spindle of range 0-10 indication is dipped into
solution, which gives some indication corresponding to the Brix present in
sample. Allow the sufficient time for the Hydrometer to reach the same
temperature as solution and then take reading. Care must be take that the
instrument floats freely and does not touch the bottom and side walls of
container when reading is taken. Read the temperature of solution using
thermometer floated in liquid. Using this indication, from standard chart brix
can be calculated by adding correction corresponding to the temperature of
sample[5.50]. This sample is then placed in the measurement cell and
corresponding output voltage of the developed FOS is noted. The remaining
samples are prepared by removing 10 ml of previously prepared sample and
add same amount of distilled water so that total volume remains 262 ml. This
procedure is repeated for getting sample containing different Brix. The
measurement of Brix using hydrometer and sensor output is done each time.

5.7.5 Results and Discussion:

Response of the sensor obtained during feasibility run is as shown in
figure 5.14 along with the curves for distilled water. A significant reduction in
output is observed with increase in molasses concentration. Further, the
typical blind, linear, non-linear nature of the curve is seen to be absent for the
molasses solutions.
Referring to model described in chapter 3 this effect was completely
new. All the sample studied till point were colorless and transparent, free from
any apparent solid content. This is the first time suspended solids were
encountered and the sample were also of deep brownish red color with
varying shades as per the concentration. The simple model of chapter 3 is
thus no more suitable to explain the sensor behavior in this situation. The dark

Chapter 5/RI Based FOCS 150

 -•—Water
-A-10%
-K-20%
-*-30%
-•-40%
-4-50%

0 1 2 3 4 5 6 7 8 9 10
x(mm)

Figure 5.14 Response of sensor for water-molasses mixture

color leads to significant absorption and suspended solids particulate matter is

responsible for scattering of light from the transmitter fiber. Both of the effects
are thus responsible for the overall reduction in the output voltage. Further,
the presence of scattering disturbs the well defined blind-linear-non-linear
nature obtained on the basis of ray optics. In fact the high degree of scattering
would couple much of light into the receiver fiber when the sensor probe-
reflector distance is small. This is in contrast to the situation in clear solutions
when the reflected cone doesn't overlap the core of receiving fiber.
Contribution of this effect would reduce as the distance increases because of
the larger fraction of absorption. It is expected that the sensor output would be
given by an expression of type
B
l(x) = Io{x)-AIn(x)+- (5.3)

where x =Sensor reflector spacing

/(x)=Sensor output at x
7o(x)=Sensor output in clear solution
A =Fraction lost due to absorption and scattering

Chapter 5/RI Based FOCS 151

 — =Fraction of light coupled in receiving fiber due to scattering
x

The scattering effect is seen to be varying inversely as distance x. this

is justified on the ground that intensity available for scattering will fall as
inverse square of x, and the number of scattering centers will increase in
proportion with x(assuming uniform density).
A simulation program implementing equation (5.3) with empirical
values of A and B supports quantitatively the observed nature of curves with
varying concentration of molasses.
Figure 5.15 shows the sensor output variations with changing
molasses concentration in an exploded form. It was observed that the sensor
gives good response for the separation of 1mm. Figure 5.16 shows the
sensor output at 1 mm of separation plotted against the concentration of
molasses. Output decreases with increase in concentration of molasses, as
the solution becomes heavy and dark in color.

0 1 2 3 4
Distance(mm)

Fig 5.15: Response of Sensor for change in

molasses concentration

Chapter 5/RI Based FOCS 152

 4.5 * •
4 !
3
> -5
0) o

~ 2.5
o
> 2
i. is
1
1 0.5
0 -I i i i

C» 10 20 30 40 50
% Molasses

Figure 5.16 Response of Sensor at x=lmm

Figure 5.17 Response of Sensor for Brix variation

Chapter 5/RI Based FOCS 153

 Figure 5.17 shows the variation of sensor output for variation Brix of
molasses samples obtained during calibration run. The Brix has been
measured using Brix hydrometer. A well defined calibration curve is obtained.
From the results presented it is seen that FO Brix refractometer
designed for BRIX measurement bears a good promise. Appropriate
mechanical probe design and circuit packaging will produce a handy
instrument suitable for field applications.

5.8 Conclusions:
Refractive index is an important characteristics of optical materials. In
this chapter the use of fiber optic sensor for refractive index variation
measurements has been demonstrated.
1. The measurements are carried out initially with developed sensor
on pure organic solvents with different refractive index. It was noted
that response of sensor is linear for variation in the variation in
refractive index of medium.
2. FO sensor is also tested using alcohol water mixtures. The mixtures
used are methanol-water, ethylene glycol-water to get a change in
refractive index. Result s obtained are matching with the reported
results in literatures.
3. The developed sensor is also used to measure the salinity of
water. It gives almost linear response for change in molarity of
NaCI salt solutions.
4. Finally response of FO sensor is observed for different
concentration of molasses. Developed sensor is used for the
measurement of Brix in the molasses.
The results obtained with developed sensor shows similarity
with simulated results and resemble physical model. Thus the
developed sensor bears a good promise. With appropriate mechanical
design and circuit packaging the developed sensors can be used in
many fields like chemical industries, food industries, sugar factory.

Chapter 5/RI Based FOCS 154

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