KINETIC STUDIES ON HYDROLYSIS OF METAL

HYDRIDE

Final year Project (MEE 499) review 2 submitted in partial fulfilment for
the award of the B.Tech degree

By
Karan Aggarwal - 14BCH0025
Dinesh Sharma - 14BCH0031
Anurag Mishra - 14BCH0073

Under the guidance of

Dr. Muruganandam L

School of Civil and Chemical Engineering (SCALE)

Vellore Institute of Technology
Vellore-632014, India
MARCH 2018
(Project Title here)
:
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 DECLARATION OF THE CANDIDATES

I hereby declare that the project report ‘Kinetic Studies on hydrolysis of Metal Hydride” is a record
of bonafide project work done by the group who carried out the project work under the guidance of
Prof. L. Muruganandam.

SIGNATURE OF THE GUIDE

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 Table of Contents

Chapter no. Title Page no.

Abstract 1

1 Introduction 2

1.1 Objective of the work 2

1.2 Literature Gap 2

1.3 Scope of the work 3

2 Experiments/Methodologies 4

2.1 Material required 4

2.2 Procedure 4

2.3 Thermodynamic analysis of the reaction 5

2.4 Experimental evaluation 6

2.5 Experimental data 7

3 Results and Discussions 9

4 Conclusion and Future work 11

5 References 12

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 Abstract

Hydrolysis of Sodium Hydride (NaH) is studied with the help of an Adiabatic Batch Reactor. This is
studied at different temperature and pressure using Modelling and Simulation of Adiabatic Batch
Reactor and relation between time, temperature and conversion is obtained. A comprehensive study of
the quantitative and qualitative aspects of the reaction and kinetic parameters related to the reaction are
obtained. Final conversion, heat of reaction and effects of temperature, NaH concentration and NaOH
concentration, effect of acidic solution and pressure on the hydrogen generation rate is being investigated.
Particular importance is given to effect of pressure, since the maximum reached pressure of hydrogen is
always substantially lower than predictions due to solubility and leakage effects when we consider 100%
conversion. Both of these effects opens up an entirely new dimensions of study, so hydrogen being the
lightest element has the highest escaping tendency. Therefore solubility of hydrogen in liquid mixture
can be good hydrogen storage system.

Keywords: hydrolysis, batch reactor, modelling, kinetic, solubility

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1. INTRODUCTION

Hydrogen economy refers to the vision of using hydrogen as a low carbon energy source. Hydrogen, as
an energy carrier is most abundant element and has the highest energy density per unit mass.

In this study, Hydrolysis of Sodium Hydride (NaH) for the production of Hydrogen is studied with the
help of an Adiabatic Batch Reactor. This is studied at different temperatures and pressures using
Modelling and Simulation of Adiabatic Batch Reactor and relation between time, temperature and
conversion is obtained.

The main aspects of hydrogen use are:- Production, Storage, Safety

1.1 Objectives of the Work

1. Study of temperature and pressure using Modelling and Simulation of Adiabatic batch reactor.
2. Study of quantitative and qualitative aspects of the reaction.
3. Effect of temperature, pressure and alkalinity on hydrogen production.
4. Study of kinetic parameters of the reaction.

1.2 Literature Gap

There are different metal and complex metal hydrides. Generation or recovery of hydrogen from hydrides
is a challenging task. Complex hydrides of lithium, magnesium and sodium are studied by different
authors but less has been said about sodium hydride therefore study on hydrolysis of sodium hydride give
valuable inputs on kinetics and related factors.
This research will also help in developing a mathematical model that captures the essence of heat and
mass transfer characteristics, which governs the discharge process. Production, storage and safety are at
the centre stage when we talk about hydrogen economy therefore analysis of sodium hydride based
Hydrogen system is developed.
Therefore to increase the storage density of hydrogen, this detailed research on application of metal
hydride (Sodium Hydride) is adopted as storage of hydrogen in metal have many advantages.

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 Kinetics of this reaction is not available in the literature, it was the main challenge to carry out the
reaction without knowing kinetics and other aspects of the reaction.

1.3 Scope of the work

Sodium Hydride is an inexpensive metal hydride that is produced in bulk and hence generally
preferred for the storage of hydrogen. Hydrogen is an ideal energy carrier which is considered for future
transport, such as automotive applications. Intensive research has been done on hydrolysis of magnesium,
aluminium, lithium etc but comparatively less study is done using sodium hydride. So a study has been
done on hydrolysis of sodium hydride to produce hydrogen gas.
Storage of hydrogen in metal have many advantages, eliminates high pressure and
cryogenic temperature storage, eliminates carbon emission observed in reforming of methane and
methanol, production of desired quantity only when required and recycling of metal hydroxide to produce
metal hydride.

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2. Experiments/ Methodologies

2.1 Materials Required

1. Adiabatic Reactor insulated with asbestos rope.

2. U tube Manometer and Thermocouple.

3. Distilled water and Sodium Hydride(NaH).

4. Stopwatch and beakers.

2.2 Procedure

Reactor is cleaned properly and dry air is purged before starting the experiment to ensure the ideal
conditions for the reaction. Ensure that temperature sensor and pressure meter are working properly.
Weigh the sodium hydride on weighing machine with at most precaution, sodium hydride is highly
hygroscopic. Before filling the distilled water we ensure all the valves are closed except water inlet ball
valve.
Water is added in the proportion of sodium hydride taken. Before adding hydride powder we insure
all the valves are closed. Powder is added and close the inlet opening. Start noting the reading of pressure
and temperature in regular intervals of time. Allow the system to reach equilibrium condition, temperature
and pressure start falling down after reaching a maximum value.
Open the needle valve to pass the gas to a baker to check how much water it displaces. After getting
Zero reading in manometer we close the valve and left it for sometime. After 15-20 min again we noted
the pressure reading. There was significant pressure developed.
We take out the mixture of water and sodium hydroxide from drain valve and calculate the volume
obtained. Clean pipette, burette, test tube and other equipments used in titration. Prepare a dilute solution
of HCl after adding water of particular amount and fill it in burette with the help of a funnel. Take 20 ml
of HCl solution obtained from reactor in beaker and add 1-2 drops of Phenolphthalein indicator which
turns the solution pink in colour.
Titrate the solution and record the end point when solution turns colourless to pink. Now clean the
equipment to make it ready for next round of experiment with different amount of water and metal hydride.

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2.3 Thermodynamic Analysis of the reaction

2.31 Rate equation in terms of concentration

𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷

𝑟𝐴 = −𝐾𝐶 𝑛

K → rate constant
n → order of the reaction
c → concentration

2.32 Enthalpy Calculations (At any temperature)

NaH + H2 O → NaOH + H2

298K ° ° ° °
∆Heq = ∆HH 2
+ ∆HNaOH − ∆HNaH − ∆HH 2O
= −416.88 + 56.44 + 285
= −84.44 KJ/mol
∆H = ∆H ° + ∫ (CPNaOH + CPH2 − CPNaH − CH2 O )
T

∆H = ∆H ° + ∫(302.77) − (106.82964 × 10−3 T) + (3248.384 − 48 × 10−6 T 2 )

298
2
− (2485.8 − 941 × 10−9 T 3 ) − (3.6505920 × 106 ⁄T )
2
− (2485.8 − 941 × 10−9 T 3 ) − (3.6505920 × 106 ⁄T ) dT

2.34 Gibbs Energy Calculations (At any temperature)

°
298K
∆Geq = ∆𝐺𝐻° 2 + ∆𝐺𝑁𝑎𝑂𝐻 °
− ∆𝐺𝑁𝑎𝐻 − ∆𝐺𝐻° 2 𝑂
= −419.2 + 33.5 + 237.14
= −148.56 KJ/Kmol
∆𝐺 = −174031218 − 0.30277218 𝑇 𝑙𝑛𝑇 + 0.804148 × 10−3 𝑇 2 − 0.54139 × 10−6 𝑇 3 − 𝐴𝑅𝑇
°

25.75 − 0.30277 × 298 × ln298

= 0.8044 × 10−3 × 298 × 298 − 0.54139 × 0.298 × 0.298 × 298 − 𝐴𝑅
AR = 1.61
°
∆𝐺 = −174.031218
− 0.30277218 𝑇 ln 𝑇 − 0.804148 × 10−3 𝑇 2 − 0.54139 × 10−6 × 𝑇 3
− (1.61)𝑇

2.35 Keq relation with temperature

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 𝑙𝑛𝐾𝑒𝑞 = −∆𝐺/𝑅𝑇

𝑙𝑛𝐾𝑒𝑞 = (−174.031218
− 0.30277218 𝑇 ln 𝑇 − 0.804148 × 10−3 𝑇 2 − 0.54139 × 10−6 × 𝑇 3
− (1.61)𝑇)/𝑅𝑇

2.36 Relation between Rate constant and Keq

𝑙𝑛𝐾 = 𝑙𝑛𝑇 + 𝑙𝑛𝐾𝑒𝑞

From Thermodynamic analysis we can get Keq data which we can use to verify practical Keq from
practical data.

2.4 Experimental evaluation of Keq

𝑁𝑎𝐻(𝑠) + 𝐻2 𝑂(𝑙) ↔ 𝑁𝑎𝑂𝐻(𝑎𝑞) + 𝐻2 (𝑔)

𝐶𝑁𝑎𝑂𝐻 𝐶𝐻2
𝐾𝑒𝑞 = 𝐾𝐶 =
𝐶𝑁𝑎𝐻 𝐶𝐻2 𝑂

CNaOH is obtained after titration of remaining reactant product mixture with HCl

2.41 Evaluation of order of the reaction

𝑑𝑇 −∆𝐻
= 𝑟
𝑑𝑡 𝜌𝐶𝑃

𝑑𝑃𝐻2
=𝑟
𝑑𝑡

Δ𝐻 → 𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝑇 → 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
𝑡 → 𝑡𝑖𝑚𝑒
𝜌 → 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑖𝑥𝑡𝑢𝑟𝑒
𝐶𝑃 → 𝑆𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝐻𝑒𝑎𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑖𝑥𝑡𝑢𝑟𝑒
𝑟 → 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

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 2.5 Experimental data

Series of experiments were conducted with different proportion of NaH concentration.

Table 1
Amount of NaH= 0.24 g(in 50 ml water)

S.no Time(Sec) T (K) P(mm Hg ) P(psi)

1 0 298 0 0

2 5 299 9 0.171

3 10 299.7 17 0.323

4 15 300.2 23 0.437

5 20 300.7 27 0.513

6 25 301.1 31 0.589

7 30 301.6 33 0.627

8 35 301.8 36 0.684

9 40 301.9 37 0.703

10 45 302 38 0.722

11 50 302 39 0.741

12 55 302 39 0.741

13 60 302 39 0.741

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 Table 2
Amount of NaH= 0.3 g(in 50 ml water)

S.no Time(Sec) T (K) P(mm Hg ) P(psi)

1 0 298 0 0

2 5 299.3 11 0.209

3 10 300.1 21 0.399

4 15 300.9 28 0.532

5 20 301.5 34 0.646

6 25 301.9 38 0.722

7 30 302.2 41 0.779

8 35 302.5 43 0.817

9 40 302.8 44 0.836

10 45 302.9 46 0.874

11 50 303 47 0.893

12 55 303 47 0.893

13 60 303 47 0.893

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 Table 3
Titration Readings

S.no Volume of Concentration of Volume of Concentration of Amount of

NaOH (ml) HCl (N) HCl(ml) NaOH(N) NaOH(g)
1 100 0.1 8.5 0.0085 0.336
2 100 0.1 11.2 0.01125 0.45

3. Results and Discussion

3.1 Temperature vs Time (Amount of NaH= 0.24 g(in 50ml water))

Temperature (K) vs Time(Sec) for 0.24gm

0.8

0.7

0.6

0.5
T(K)

0.4

0.3

0.2

0.1

0
0 10 20 30 40 50 60 70
Time(Sec)

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 3.2 Pressure vs Time (Amount of NaH= 0.3 g(in 50 ml water))

Pressure (Psi) vs Time(Sec) for 0.24gm

0.8

0.7

0.6

0.5
P(Psi)

0.4

0.3

0.2

0.1

0
0 10 20 30 40 50 60 70
Time(Sec)

3.3 Temperature vs Time (Amount of NaH= 0.3 g (in 50 ml water))

T (K) vs Time(Sec) for 0.3gm
304

303

302

301
T(K)

300

299

298

297
0 10 20 30 40 50 60 70
Time(Sec)

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 3.3 Pressure vs Time (Amount of NaH = 0.3 g(in 50 ml water)
Pressure(psi) Vs Time(sec)
1

0.9

0.8

0.7

0.6
P(Psi)

0.5

0.4

0.3

0.2

0.1

0
0 10 20 30 40 50 60 70
Time(Sec)

4. Conclusion and Future work

4.1 Conclusion

1. As we see from the obtained graphs, pressure is more in the second plot which has more
concentration of NaH so we conclude that this reaction has positive order in terms of NaH.

2. Modeling of the adiabatic batch reactor is done.

3. Effects of Temperature and Pressure on hydrogen generation are studied and analysed
through graphs and plots.

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4.2 Future Work

1. More experiments with different concentrations are to be performed in order to get

experimental data.

2. Simulation of modelled equations is to be done.

3. More kinetic parameters of the reaction need to be studied.

5. References

1. I.V. Drozdov* , V. Kochubey, Li Meng, G. Mauer, R. Vaßen, D. Stover, Modelling and

proper evaluation of volumetric kinetics of hydrogen desorption by metal hydrides,
International Journal of Hydrogen Energy, 40 (2015), 10111-10122
2. P. B. Terent’eva , E. G. Gerasimova , N. V. Mushnikova , M. A. Uimina , V. V. Maikova ,
V. S. Gavikoa , and V. D. Golovatenkob, Kinetics of Hydrogen Desorption from MgH2
and AlH3 Hydrides, The Physics of Metals and Metallography, 116 (2015), 1197–1202
3. I.E. Gabis, I.A. Chernov , A.P. Voyt, Decomposition kinetics of metal hydrides:
Experiments and modelling, Journal of Alloys and Compounds, 580 (2013), S243–S246

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 4. Marco Gambini, Tommaso Stilo* , Michela Vellini, High temperature metal hydrides for
energy systems Part B: Comparison between high and low temperature metal hydride
reservoirs, International Journal of Hydrogen Energy xxx (2017), 1-11
5. V.C.Y. Konga, D.W. Kirka, F.R. Foulkesa, J.T. Hinatsub, Development of hydrogen
storage for fuel cell generators II: utilization of calcium hydride and lithium hydride,
International Journal of Hydrogen Energy, 28 (2003), 205 – 214
6. A.M.F.R. Pintoa, D.S. Falcãoa, R.A. Silvab, C.M. Rangelb, Hydrogen generation and
storage from hydrolysis of sodium borohydride in batch reactors, International Journal of
Hydrogen Energy, 31 (2006), 1341 – 1347
7. Billur Sakintunaa, Farida Lamari-Darkrimb, Michael Hirscherc, Metal hydride materials
for solid hydrogen storage: A review, International Journal of Hydrogen Energy, 32 (2007),
1121 – 1140
8. J. S. Han , M. Pezat, Jai-Young Lee, Thermal Desorption Of Hydrogen From Magnesium
Hydride, Scripta Metallurgica Pergamon Journals Ltd., 20 (1986), 951-956
9. H. Scott Fogler, Elements of Chemical Reaction Engineering, 3rd Edition, Prentice Ha
ll International Series, (2000)
10. Octave Levenspiel, Chemical Reaction Engineering, 3rd Edition, John Wiley & Sons,
(1999)

J. Philip DiPietro; Edward G. Skolnik (October 1999). "Analysis of the Sodium Hydride-based Hydrogen Storage System
being developed by PowerBall Technologies, LLC" (PDF). US Department of Energy, Office of Power Technologies.
Retrieved 2009-09-01.

Kinetic studies on the NaBH4/H2O hydrogen storage system with CoCl2 as a catalyst

A. Kaur*
, D. Gangacharyulu, P.K. Bajpai
Department of Chemical Engineering, Thapar University, Patiala, India
Received April 28, 2015, Revised September 26, 2015

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