AU2021106404A4

AU2021106404A4 - A frequently transesterification process of Jatropha curcus oil in the presence of a green solvent

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Publication number: AU2021106404A4
Application number: AU2021106404A
Authority: AU
Inventors: Deepak Birla; Mohit Chaturvedi; Sachin Chordia; Jeetu Gangil; Girendra Gautam; Gajendra Kumar; Ravi Kumar; Satendra KUMAR; Neeraj Patidar; Vikas Sharma; Abhishek Tiwari; Vikrant Verma
Original assignee: Birla Deepak Dr; Chaturvedi Mohit Dr; Chordia Sachin Prof; Gangil Jeetu Dr; Gautam Girendra Dr; Kumar Gajendra Dr; Kumar Ravi Mr; Kumar Satendra Dr; Patidar Neeraj Mr; Sharma Vikas Dr; Verma Vikrant Dr
Current assignee: Birla Deepak Dr; Chaturvedi Mohit Dr; Chordia Sachin Prof; Gangil Jeetu Dr; Gautam Girendra Dr; Kumar Gajendra Dr; Kumar Satendra Dr; Sharma Vikas Dr; Verma Vikrant Dr
Priority date: 2021-08-22
Filing date: 2021-08-22
Publication date: 2021-11-25
Anticipated expiration: 2029-08-22

Abstract

A FREQUENTLY TRANSESTERIFICATION PROCESS OF JATROPHA CURCUS OIL IN THE PRESENCE OF A GREEN SOLVENT 5 A quality improver and environmental friendly system for fast transesterification of Jatropha curcus oil was developed for the production of biodiesel using a continuous coil flow reactor at 70°C in the presence of a green solvent with potassium hydroxide as a catalyst. When the oil to methanol molar ratio was 1:5, catalyst concentration 0.75 wt% of oil and flow rate 250 m/min, transesterification was completed within 1.62 minute. The purity and conversion of biodiesel was .0 99.040.05% analyzed by the reverse phase HPLC method. 14 Circulating water bath 70°C Reactor R2, at 70' eco 3 t7° (5mmn 1.D. x 5m) (5mmit 1.D. x 5m) Reactor R4, at 70°C (5mmlt I.D. x 5m) Separating funnel Seprating funnel Condenser S1 S3at 15°C Reactor RI, at 70°C Sepratmg funnel (5mm 1.D1 x 5m) S2 Peri taltic Per tactic Per .taltic pun s P3 pun s P2 pun ps P1 ResevoirC Resevoir B Resevoir A Fig.1. Schematic diagram of continuous tranaesterification of Jatropha curcus oil using coil flow reactor. 15

Description

Circulating water bath

70°C Reactor R2, at 70' eco 3 t7° (5mmit 1.D. x 5m) Reactor R4, at 70°C (5mmn 1.D. x 5m) (5mmlt I.D. x 5m)

Separating funnel Seprating funnel Condenser S1 S3at 15°C Reactor RI, at 70°C Sepratmg funnel (5mm 1.D1 x 5m) S2 Peri taltic Per tactic Per .taltic pun s P3 pun s P2 pun ps P1

ResevoirC Resevoir B Resevoir A

Fig.1. Schematic diagram of continuous tranaesterification of Jatropha curcus oil using coil flow reactor.

TITLE OF THE INVENTION

A frequently transesterification process of Jatropha curcus oil in the presence of a green solvent

FIELD OF THE INVENTION

This invention relates to A frequently transesterification process of Jatropha curcus oil in the

presence of a green solvent.

BACKGROUND OF THE INVENTION

The reduction of greenhouse gas emission has become an important and crucial step in fulfilling

the requirements mandated under the Kyoto protocol. Depletion of the world petroleum reserves

and increasing environmental concerns have stimulated the search for renewable fuels (Shay.,

.0 1993). Among the various types of alternative fuels produced from renewable resources, biodiesel,

which is derived from the oils and fats of plants and animals, has attracted considerable attention

over recent decades as a renewable, biodegradable, eco-friendly and non-toxic fuel. Other

advantage of the biodiesel is its good lubrication property that extends the engine life, its high flash

point and acceptable cold filter plugging point (CFPP) makes it very attractive as an alternative

.5 fuel, is currently becoming a fast-growing market product (Ramadhas et al., 2005; Wang et al.,

2006; Mittelbach, 1996; Mittelbach and Enzelsberger, 1999; Park et al., 2008a). Low viscosity of

fatty acid methyl esters (FAMEs) are significantly lower than the oils (Clark et al., 1984), thereby

reducing droplet size upon injection into the cylinder and facilitating combustion. Cetane indices

and gross heat of combustion per unit weight (Kanit., 1991; Saho et al., 2007) of fatty acid methyl

esters are slightly higher than oils. FAMEs have lesser tendency to polymerize three dimensionally

than the oils.

Different methods of synthesizing biodiesel have been proposed. The most common way

is the catalytic transesterification reaction of vegetable oils with a short chain alcohol, usually methanol, also known as methanolysis; this reaction is well studied and established for soybean, sunflower, Jatropha curcus and rapeseed oil, using acid or alkali as catalyst (Funguri et al., 1999).

John and Marvin 1954 have reported that transesterification proceeds rapidly in the presence of

alkaline catalyst and that reaction are about 4000 times faster than those catalyzed by the same

amount of acidic catalyst. Heterogeneous catalytic transesterification reaction requires drastic

condition and longer reaction time periods (Young et al., 2010; Kumar et al.,2010). Continuous

transesterification also has been reported (Kumar et al., 2010). In this paper, we reported a rapid

frequently transesterification in the presence of a mutual green solvent (Jatropha curcus biodiesel)

for methanol and Jatropha curcus oil. Biodiesel is a good solvent for vegetable oil and miscible

.0 with methanol. Thus, it is accepted that solvent may help increases the solubility of methanol and

oil in the reactor and promote transesterification.

SUMMARY OF THE INVENTION

A quality improver and environmental friendly system for fast transesterification of Jatropha

curcus oil was developed for the production of biodiesel using a continuous coil flow reactor at

.5 70oC in the presence of a green solvent with potassium hydroxide as a catalyst. When the oil to

methanol molar ratio was 1:5, catalyst concentration 0.75 wt% of oil and flow rate 250 ml/min,

transesterification was completed within 1.62 minute. The purity and conversion of biodiesel was

99.04+0.05% analyzed by the reverse phase HPLC method.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig.1. Schematic diagram of continuous tranaesterification of Jatropha curcus oil using coil flow

reactor.

Fig.2. Effect of catalyst concentration and molar ratio (oil to MeOH) on conversion of Jatropha

curcus oil to methyl esters (reaction temp. 70oC, flow rate 250 ml/min).

Fig.3. Effect of solvent concentration and reaction temperature on conversion of Jatropha curcus

oil to methyl esters (catalyst concentration 0.75, molar ratio oil to MeOH 1:5, flow rate 250

ml/min)

Fig.4. HPLC chromatogram of (A) Jatropha Curcus oil showing presence of different

triglycerides. (B) Biodiesel of Jatropha Curcus oil showing presence of different fatty acid methyl

esters.

Fig. 5. Calibration curve of pure standards of (A) MeL and (B) MeO. HPLC condition: UV

detection at 215 nm, injection volumes 5 pL. Other condition as determined in section 3.5.

DETAILED DESCRIPTION OF THE INVENTION

.0 2. Experimental

2.1. Material

Commercial grades Jatropha curcus oil was procured from local market purchase, methanol

(purity 98%) and KOH (purity 85%) were used from M/S Ranbaxy. According to ASTM the acid

value of the Jatropha curcus oil was 1.3 to 1.8 mg KOH/gm sample. Initial composition of oil

.5 analyzed by HPLC was Triglycerides (TG) 96.5 wt%, Diglycerides (DG) 3 wt% and

monoglycerides (MG) 0.5 wt%. Physico chemical characterization of oil is given in table 1.

2.2. Experimental set-up andprocedure

Experimental set-up for frequently transesterification of Jatropha curcus oil(Pretreated, acid value

0.5) was carried out in a continuous coil flow glass reactor as shown infig 1. Three reservoir A, B

and C were used, reservoir A used to store 10% green solvent (Jatropha curcus biodiesel) diluted

Jatropha curcus oil and another two reservoirs B and C were used to storage two solution of

alcoholic KOH at different concentration 0.50% and 0.25 wt% of oil, respectively. Three peristaltic

pumps P1, P2 and P3 that could run various continuous speeds were used to deliver reactants in insulated reactors. Pump P1 deliver diluted Jatropha curcus oil from reservoir A to reactor first and pump P2 and P3 were used to delivered alkali solution from reservoir B and C to reactor first and third at different flow rate 3 moles and 2 moles, respectively. In this experiment four continuous coil flow reactor are joined in series at different height (inner diameter and length of each coil 5mm ID x 5 meters length). In the coils baffle are fixed in a circular path and distance between the two baffles was 2 cm. Three separating funnels were attached after second, third and fourth reactor, respectively for the separation of glycerol by the downstream process. All coils were immersed in a water condenser type hot glass tube set at 70°C with the help of circulating water bath. In the end product was passed through a condenser at room temp 15°C and finally

.0 product was collected in a collector. The catalyst was removed by warm water washing. The

complete removal of catalyst was checked by phenolphthalein indicator. Tracer of moisture and

unreacted alcohol were removed by vacuum distillation. Finally esters were dried over anhydrous

sodium sulphate and analyzed by HPLC method.

3. Results and Discussion

.5 3.1. Catalysttype and concentration

Catalyst used for the transesterification of vegetable oils are classified as alkali, acid, enzyme

and heterogeneous catalysts, among of which alkali catalysts like sodium hydroxide, potassium

hydroxide and potassium methoxide are more effective. If the oil has high FFA and water content

acid catalyzed transesterification is suitable. As a catalyst in the process of alkaline methanolysis

mostly sodium hydroxide or potassium hydroxide has been used when the oil has less than 1%

FFA.

The typical present work continuous transesterification of Jatropha curcus oil, alkaline catalyst

is more suitable due to the presence of low FFA. In the methanolysis of Jatropha curcus oil with potassium hydroxide gives the best results. In this process flow rate was 250 ml/min, temperature

70°C and molar ratio oil to methanol 1:5 was held constant, fig. 2 summarized the effects of

variation in catalyst concentration from0.25 to 1.0 wt% of oil. Optimization of catalyst percentage:

when catalyst percentage was 0.25% gives 75% conversion biodiesel, after increasing the catalyst

percentage the conversion was increased at 0.75 wt% catalyst (KOH) gives the best conversion

99.04 0.05%. There are many drawbacks in the excessive use of alkaline catalyst in the

transesterification reaction. Higher catalyst concentration increases the solubility of methyl esters

in the glycerol phase of the final product. As a result, a significant amount of methyl esters remain

in the glycerol layer after the phase separation.

.0 3.2. Molar ratio

One of the most important variables affecting the yield of ester is the molar ratio of alcohol to

oil. The stoichiometric ratio for transesterification required three moles of alcohol and one mole

of triglyceride to yield the three moles of fatty acid methyl esters and one mole of glycerol.

However, transesterification is a reversible reaction in which a high molar ratio is used to drive

.5 the reaction to the forward direction, enhance the solubility and to increase the contact between

the triglycerides and alcohol molecule. Experiments were conducted with molar ratios of oil to

methanol 1:3, 1:4, 1:5 and 1:6 for catalyst concentration 0.75 wt% of oil. The experimental data

are presented in Fig. 2. In the present work at the molar ratio 1:5 the conversion of triglycerides

was maximum > 99%. In this experiment methanol feeds in two parts 3 moles and 2 moles in

reactor first and third, respectively. Molar ratio shows no effect on acid, peroxide, saponification

and iodine values of methyl esters (Tomasevic et al., 2003). However, the high molar ratio of

alcohol to vegetable oil interferes with the separation of glycerol because there is an increase in

solubility.

3.3. Effect of reaction temperature

The conversion of Jatropha curcus oil in to fatty acid methyl esters increases with reaction

temperature. Experimental trials were carried out at 25°C (room temperature), 65°C, 70°C and

75°C. In all experiments oil to methanol ratio was constant 1:5 and 0.75 wt% KOH (as catalyst)

were used (the optimal condition achieved in the previous section). The yield of methyl ester at

room temperature and 65°C were 42% and 92%, respectively. The maximum conversion >99% is

obtained at the temperature 70°C. Fig. 3 indicates the results of these experiments; methanolysis

of vegetable oil is normally performed near the boiling point of the alcohol.

3.4. Effect offlow rate

.0 In the process of continuous transesterification of Jatropha curcus oil experiments were

optimized at total flow rate ranging from 200 ml/min to 275 ml/min, all experiments were

conducted with catalyst concentration 0.75 wt% of oil, molar ratio of oil to methanol 1:5 and

reaction temperature 70°C (the optimal condition achieved in the previous sections). The effects

of total flow (oil+MeOH) rate and residence time are given in table 2, when the total flow rate of

.5 oil and MeOH was 250 ml/min (207 ml oil and 43 ml MeOH). It gives the best conversion >99%

and production of biodiesel was 13.17 L/hr.

3.5. Effect ofgreen solvent concentration

The influence of solvent on fatty acid methyl esters (FAMEs) yield is shown infig.3. The

experimental trials were carried out at different concentration of green solvent (biodiesel). The

maximum fatty acid methyl esters yield could be obtained at the concentration of solvent 7wt% of

oil. Biodiesel is a good solvent for vegetable oil and miscible with methanol. Thus, it is expected

that biodiesel may help mix methanol and oil in the reactor coils and increase rate of reaction.

3.5. HPLCAnalysis

HPLC was used to analyze the purity, conversion and FAMEs composition of the biodiesel

esters sample. The Reverse phase high performance liquid chromatography (RP-HPLC) separates

different components according to their polarity. The chromatographic apparatus consisted of a

model waters 600 pump with waters 600 controller, waters 2,996 photodiode array detector, a

nova-pack, 3.9 x 150 mm column with guard column of dimension 3.9 x 20 mm, both packed

with C18 particle with diameter 4 im. (all from waters, Milford MA, USA).

HPLC condition: RP-HPLC method flow rate of iml/min, an injection volume of5pl, a column

temperature of 45 °C, the UV detection at 215 nm and a 40 min gradient mobile phase 15% H 2 0

+ 85% CH 30H in 10 min, 100% CH 30H in 0 min, 60% CH3 0H + 15% hexane + 25% propane

.0 2o1 in 30 min and for the last 10 min system back to initial state 15% H 2 0 + 85% CH30H were

used for the separation and determination of the compound produced during the methanolysis of

Jatropha curcus oil in all the experiments Fig. 4 shows the HPLC separation of oil (A) and

biodiesel (B), respectively. The fatty acids compositions of Jatropha curcus oil are given in Table

3.

.5 Calibration curves were generated for two standards (Sigma Aldrich) methyl oleate and methyl

linoleate. Each data point was obtained from at least two repeated measurements. Stock solutions

of the standards were prepared as about 5 mg/ml in hexane, and then serial dilution were made as

required. Relative integrated peak area versus injected amount of the methyl ester standard was

plotted for MeO and MeL. The calibration curves (relative peak area versus concentration are

shown in Fig. 5) of the standards showed good linearity (R 2 =0.999).

4. Characterization

4.1. Kinematic Viscosity, Acid number and oxidation stability

All the physicochemical properties are given in Table 4. The kinematic viscosity of biodiesel

at 40°C was determined following ASTM D 445 using a Rheotek AKV 800 automated kinematic

viscometer (Poulten Selfe and Lee Ltd., Essex, England). The acid number of biodiesel was

determined according to ASTM D 664 using a Brinkman/Metrohn 809 Titrando (Westbury, NY).

The oxidation stability of biodiesel was determined as the induction period (IP) according to EN

14112 using a Metrohn 743 Rancimat instrument (Herisau, Switzerland).

4.2. Coldflow properties

The cloud point (CP), pour point (PP) and cloud filter plugging point (CFPP) measurements

were done as per ASTM standers, D 2500-05, D 97-96a and D 6371-05 , respectively .A Lawler

.0 model DR-34H automated cold properties analyzed (Lawler Manufacturing Corporation, Edison,

NJ) was used to measure the cold flow properties.

Conclusion

The present study results indicate that the optimum reaction condition for frequently

methanolysis of Jatropha curcus oil using coil flow reactor i.e., 0.75% KOH as catalyst (wt% of

.5 oil), reaction temperature 70°C, oil/methanol molar ratio 1:5 and residence time 1.62 min gives

>99% conversion and production of biodiesel 13.17 L/hr. The synthesized biodiesel match ASTM

and BIS specification (table 4). The purity and quality of synthesized biodiesel were checked by

the HPLC methode.

Table 1. Physico chemical characterization of Jatropha curcus oil.

Density at 15°C 0.918 gm/cm3

Refractive index (nD 40'C) 1.484

Molecular weight 888

Kinematic viscosity at 40°C 34.33 c St

Saponification value 199 mg KOH/gm oil

Acid value 0.5 mgKOH/gm oil (after pretreatment of oil)

Cetane number 23

Flash point 186

Table 2. Effect of flow rate and residence time on yield of Jatropha curcus oil to methyl esters. (Molar ratio oil to methanol 1:5, catalyst concentration 0.75 wt% of oil, reaction temperature 70 C). Flow rate (ml/min) Residence time (min) Conversion

% Oil MeOH Total Reactor Reactor Reactor Reactor Tota Sl S2 S3 (ml) (ml) (ml) (RI) (R2) (R3) (R4) 1 166 34.38 200.38 0.52 0.52 0.49 0.49 1.93 61.5 97.0 99.4 0 186. 38.63 225.13 0.46 0.46 0.43 0.43 1.73 60.5 96.8 99.4 5 1 207 42.88 249.88 0.42 0.42 0.39 0.39 1.62 60.2 96.8 99.4 1 228 47.23 275.23 0.38 0.38 0.35 0.35 1.48 45.8 80.0 85.6 0 S = Separating funnel First, S2 = Separating funnel second, S3 = Separating funnel third.

Table 3. Fatty acid methyl esters (FAME) composition of Jatropha curcus oil based biodiesel.

Fatty acid Percentage

Palmitic (C16) 15.82

Linolenic (C18:3) 0.73

Linoleic (C18:2) 30.56

Oleic (C18:1) 44.21

Stearic (C18:0) 8.15

Table 4. Physico chemical characterization of Jatropha curcus biodiesel.

Property ASTM ASTM BIS Biodiesel method Specification Specification

Viscosity 40°C (mm2 /s) D 445 1.9-6.0 2.5-6.0 3.88

Acid number (mgKOH/g) D 664 0.5 <0.5 0.18

Free glycerin (mass %) D 6584 0.020 ---- 0.008

Total glycerin (mass %) D 6584 0.24 ---- 0.24

Oxidation stability (IP, h) EN 14112 3 minimum ---- 5.0

Cloud point D 2500-05 -3 to +12 ---- -5

Pour point D 97-96a -15 to +10 ---- -12

Cetane number D 613 >47 >51 54

Cold filter plugging point D 6371 -4 to -9 ---- -1

Density at 15°C (Kg/m3) D 976 0.575 to 0.900 0.860-0.900 0.8633

Flash point (°C) D 93 >100 >120 135

Carbon residue (wt%) D 4530 <0.02 <0.02 0.005

Copper strip corrosion D6751 <No. 1.0 1.0 1.0

(3 hrs at 100°C)

Water content (ppm) D 95 <500 <500 230

References

Clark, S.J., Wagner, L., Schrock, M.D., Piennaar, P.G., 1984. Methyl and ethyl soybean esters as

renewable fuels for diesel engines. JAOCS 61, 1632-1638.

Fangrui, M., Milford, A.H., 1999. Biodiesel production: a review. Bioresource Technology 70, 1

15.

John, N.S., Marvin, W.F., 1954. Saponification value determination of difficultly saponifiable

drying oil products. JAOCS 31, 448-451.

Kanit, K., 1991. Estimation of heat of combustion of triglycerides and fatty acid methyl esters.

JAOCS 68,56-58.A.

Kumar, G., Kumar, D., Singh, S., Kothari, S., Bhatt, S., Singh, C.P., 2010. Continuous low cost

transesterification process for the production of coconut biodiesel. Energies 3, 43-56.

Kumar, D., Kumar, G., Poonam., Singh, C.P., 2010. Ultrasonic-assisted transesterification of

Jatropha curcus oil using solid catalyst, Na/SiO2. Ultrasonic Sonochemistry, DOI

10.1016/j.ultsonch.2010.03.001.

Mittelbach, M., 1996. Diesel fuel derived from vegetable oil, VI: specifications and quality control

of biodiesel. Bioresource Technoloy 56, 7-11.

.0 Mittelbach, M., Enzelsberger, H., 1999. Transesterification of heated repeseed oil for extending

diesel fuel. JAOCS 76, 545-550.

Park, Y.-M., Lee, J.Y., Sang, H.C., Park, I.S., Lee, S.Y., Deog, K.K., Lee, J.S., Lee, K.Y., 2010.

Esterification of used vegetable oils using the heterogeneous W03/ZrO2 catalyst for

production of biodiesel. Bioresource Technology 101, S59-S61.

.5 Park, J.Y., Kim, D.K., Lee, J.P., Park, S.C., Kim, Y.J., Lee, J.S., 2008a. Blending effects of

biodiesel on oxidation stability and low temperature flow properties. Bioresource

Technology 99, 1196-1203.

Ramadhas, A.S., Jayaraj, S., Muraleedharan, C., 2005. Biodiesel production from high FFA rubber

seed oil. Fuel 84, 335-340.

Say, E.G., 1993. Diesel fuel from vegetable oil: status and opportunities. Biomass Bioenergy 4,

227-242.

Saho, P.K., Das, L.M., Baba, M.K.G, Naik, S.N., 2007. Biodiesel development from high acid

value polange seed oil and performance evolution in C.I. engine. Fuel 86, 448-456.

Tomasevic, A.V., Marinkovic, S.S., 2003. Methanolysis of used frying oils. Fuel Proc.

Technology 81, 1-6.

Wang, Y., Ou, S., Liu, P., Xue, F., Tans, S., 2006. Comparison of two different processes to

synthesize biodiesel by waste cooking oil. Journal of Molecular Catalysis A: Chemical

252, 107-112.

ASTM D 445-06., 2006. Standard test method for kinematic viscosity of transparent and opaque

(and calculation of dynamic viscosity). In Annual book of ASTM Standard; ASTM:

Philadelphia.

ASTM D 664-06., 2006. Standard test method for acid number of petroleum products by

.0 potentiometric titration. In Annual book of ASTM Standard; ASTM: Philadelphia.

EN 14112., 2003. Determination of oxidation stability (accelerated oxidation test). European

Committee for Standardization: Brussels.

ASTM D 2500-05., 2006. Standard test method for cloud point of petroleum product. In Annual

book of ASTM Standard; ASTM: Philadelphia.

.5 ASTM D 97-96a., 1996. Standard test method for pour point of petroleum product. In Annual book

of ASTM Standard; ASTM: Philadelphia.

ASTM D 6371-05., 2006. Standard test method for cold filter plugging point of diesel and heating

fuels. In Annual book of ASTM Standard; ASTM: Philadelphia.

Claims

CLAIMS:

1. A method of transesterification of Jatropha curcus oil, alkaline catalyst is more suitable due to

the presence of low FFA.

2. The method as claimed in claim 1, wherein in the methanolysis of Jatropha curcus oil with

potassium hydroxide gives the best results.

3. The method as claimed in claim 1, wherein in this process flow rate was 250 m/min,

temperature 70°C and molar ratio oil to methanol 1:5 was held constant.

4. The method as claimed in claim 1, wherein the effects of variation in catalyst concentration

from 0.25 to 1.0 wt% of oil; and Optimization of catalyst percentage: when catalyst percentage

was 0.25% gives 75% conversion biodiesel, after increasing the catalyst percentage the

conversion was increased at 0.75 wt% catalyst (KOH) gives the best conversion 99.04 0.05%.

Fig.2. Effect of catalyst concentration and molar ratio (oil to MeOH) on conversion of Jatropha curcus oil to methyl esters (reaction temp. 70oC, flow rate 250 ml/min).

Fig.3. Effect of solvent concentration and reaction temperature on conversion of Jatropha curcus oil to methyl esters (catalyst concentration 0.75, molar ratio oil to MeOH 1:5, flow rate 250 ml/min)

(A)

(B)

Fig.4. HPLC chromatogram of (A) Jatropha Curcus oil showing presence of different triglycerides. (B) Biodiesel of Jatropha Curcus oil showing presence of different fatty acid methyl esters.

(A)

(B)

Fig.

5. Calibration curve of pure standards of (A) MeL and (B) MeO. HPLC condition: UV detection at 215 nm, injection volumes 5 µL. Other condition as determined in section 3.5.