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- Thermodynamics Solution
- 5416833 the Problem of Physic
- RPT ScYr5
- 06_part1d
- Physics 2C Syllabus
- PROB SET
- Feynman Analysis Ratchet Engine
- Entropy
- Introduction for fundamentals english
- ChEmeng
- Basic Physics
- Second Law of Thermodynamics
- Eva Cool
- exweek3
- Pg Brochure 2014
- 231520479 the PE Exam Survival Guide (1)
- Thermodynamics 1
- Statistical Physics
- Gas Dynamics-Module I
- hw2soln

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1/28

Simple tests

To be done after reading and learning the lecture.

Content :

Chapter I................................................................................................................................. 2

Chapter II ............................................................................................................................... 4

Chapter IV.............................................................................................................................. 7

Chapter V ............................................................................................................................... 9

Chapter VI............................................................................................................................ 16

Chapter VII........................................................................................................................... 20

Chapter IX............................................................................................................................ 23

january 2011

2/28

Chapter I

Pressure and temperature

The ideal gas

1. What are the different assumptions used to define the ideal gas ?

2. Define the so-called "standard and normal conditions of temperature and pressure". What is

the molar volume of gas in such conditions ? Find the value of the universal gas constant in

SI. What is the unit ?

3.An electronic tube is sealed under vacuum at 27C under a pressure of 1.2 10-5 torr. The

volume of the tube is equal to 100 cm3. How many molecules are trapped in the tube ?

4.A given quantity of gas fills a volume of 200 cm3 at CNTP. What would be the volume at

273C under 4 atm ?

6.What is the specific gravity with respect to air of carbon monoxide under 2.5 atm at -20C ?

7.A mixture of gases is made of 65wt% nitrogen, 15wt% hydrogen, and 20wt% carbon

dioxide. The total pressure is 760 torr. Give the molar fractions of the three gases. Calculate

the partial pressures.

dihydrogen is injected in a florence flask of 22.4 L, initially filled with air under 1 atm. The

temperature is maintained constant at 0C. What is the mean molar weight of the airdihydrogen mixture ?

(a) atmosphere, (b) torr, (c) bar.

3/28

Answers

P V T0

6.02 1023

3.86 1013 ;

760 22.4 300

P0 V0 T

3-

N = NA

4-

V V0

P0 T

50 cm3 ;

P T0

5-

P T0

16 4 273

2.6 g litre1 ;

22.4 1 300

P0 T

6-

The specific gravity with respect to air is independent on the conditions of temperature

and pressure d

7-

M 28

0.966 .

29 29

xN 2 0.22

xH 2 0.712

PN 2 167 Torr

8-

nN 2 0.8

M 28

PH 2 541 Torr

nH 2 2

0,8

0,2

2

32

2 10.93g .

3

3

3

9 - 1 Torr = 133.3 Pa

xCO 2 0.068 ;

;

PCO 2 51.5Torr .

nO 2 0.20

4/28

Chapter II

Generalities

Systems, states, properties, thermodynamic processes

A. select the correct answer : "the number of compounds of a system" :

a) is always equal to the number of phases,

b) is always lower than the number of phases

c) is always larger than the number of phases

B. answer by "wrong" or "right"

a) There exists no general relationship between the number of compounds and the number of

phases of a system,

b) mixing two liquid phases, always gives one liquid phase,

c) cooling a liquid blend always gives a single solid phase, called solid solution,

d) mixing two gases always gives a single gas phase.

2- Systems

answer "right" or "wrong".

A. a closed system transfers to the surroundings :

(a) no heat

(d) no matter

(b) no work

(e) only matter

(f) only heat

C. Same question for an open system

(b) sort out intensive and extensive variables : pressure, temperature, volume, mass, electric

charge, electric potential, potential energy.

(a) volume,

(b) pressure,

(c) temperature

5- The variation of a state variable during a transformation depends on the process. Right or

wrong ?

5/28

(a) there is no exchange of work,

(b) there is no exchange of heat,

(c) there is no energy exchange,

(d) the state of the system can not be described,

(e) none of these answers above are correct (give the correct definition)

(f) the system exchanges neither work nor heat,

(g) the system initial and final states are different,

(h) matter can be exchanged

(i) braking of a vehicle,

(j) drying of clothes

(k) very slow compression of a gas by a piston sliding without friction in a cylinder.

(l) vaporisation of water at 100C under 1 atmosphere.

(m) very slow compression of gas by a piston sliding with friction against a cylinder wall.

(n) very slow traction on an elastic

(o) extension of a spring due to a mass (dropped)

(p) loading of a capacitor, previously discharged, with a battery.

9- During an isochoric process the temperature of the system remains constant. Right or

wrong ?

10- Consider a vehicle moving at a speed V (state A), then in final state B, the vehicle brakes

and stops.

A wheel of the vehicle is submitted to a process that is :

(a) isothermal,

(b) "monothermal"

(c) isobaric

(e) irreversible

(f) reversible

(g) adiabatic

(d) isochoric

11- What is the sign convention used to describe the energy exchange between a system and

the surroundings ?

6/28

Answers

1 - A a),b), c) no

2-

B) isolated system : a), b), c), d) true

C) open system : none, transfer both energy and matter

quantities are extensive.

4 - b) c) yes

5 - wrong

6 - e) closed process : identical initial and final states

7 - b)

8 - irreversible : a), b), g, h) ; quasi-static : e) ; reversible : c), d) f).

9- wrong

10- a) no, b) yes after the wheel temperature is back to 20C, c) no if one consider the stress

induced by the brake on the wheel; d) yes, if the thermal expansion of the wheel is neglected,

e) yes; f) and g) no.

7/28

Chapter IV

The first law

1- A system receives a heat quantity of 350 J. It supplies to the surroundings a work of 400 J.

What is its internal energy variation ?

altitude is 20 m. At state B the height is 10 m and the velocity is 6 ms-1. It receives a work of

25 kJ and it supplies a heat quantity of 8 kJ during the AB process. Calculate its internal

energy variation U U B U A ?

3- Right or wrong ?

a) dU dW dQ

b) U W Q

c) U W Q

d) U W Q

e) U W Q

f) dU W Q

4- Right or wrong ?

Consider a system characterised by three variables X, Y and Z related by a state equation.

a) for any process dX , dY , dZ , one can define dU dX dY dZ ,

b) for any process dX , dY , dZ , one can define dU AX BY ,

U

c) A

X X ,Y

U

d) A

Y X

U

e) A

X Y

5- Give the three hypotheses used to establish : H U nRT and the meaning of n

8/28

answers

1 - U 50 J

2- The macroscopic mechanical energy variation is

Em,macro

1

m VB2 VA2 mg (hB hA ) 16800 J

2

W Q Em,macro U

3- a) wrong

b) wrong

c) right

d) wrong

e) wrong

f) right

b) right

c) wrong :

d) wrong

e) true

9/28

Chapter V

Application of the first law

A Calorimetric coefficients

1- Give the dimensions of the coefficients CV , CP , and h in terms of the fundamental

units (length, mass, time and temperature), give the usual expression in IS units, and specify

their intensive or extensive nature.

2- We recall : C P CV

TV 2

(a) define and T . Calculate their value for an ideal gas.

(b) Show that the above general relation leads to C P CV R .

(c) given at 298 K :

H 2 O ( M 18 g ) : 2.4 104 K -1 , 1 g cm-3 , T 4.6 1010 Pa -1 , C P 75.2 Jmol-1K -1

Al

( M 27 g )

23106 K -1 ,

2.7 g cm-3 ,

T 1.331011 Pa -1 ,

C P 24.3 Jmol-1K -1

Calculate C P CV in these two above cases and compare to b)

3- Consider one mole of an ideal gas in the CNTP. What is the quantity of heat exchanged

during a reversible isothermal compression where :

(a) V 0.01 L

(b) V 10 L

(c) V 1 L

Discuss the strategy adopted to evaluate V depending on its value (use the definition of Q

or the calculation presented in B1-2.

4- Consider one mole of an ideal gas in the CNTP. What is the quantity of heat exchanged

during a reversible isothermal compression where :

(a) P 10 Pa

(b) P 5104 Pa

(a) show :

10/28

(b) express h in terms of T , and V . Calculate the numerical values of and h for water.

(c) evaluate the heat quantity during an isothermal reversible process inducing :

(i) a decrease of 0.04% of the molar volume (relative value approximately equal to that of test

3-a)

(ii) a pressure increase of 5.104 Pa (identical to test 4-b).

Compare the numerical results to those corresponding in tests 3 an 4.

6- A metallic bloc A of mass mA , molar mass M A , molar heat capacity CPA at temperature

TA is deposited on a bloc B ( mB , M B , CPB , TB ), so that they are in contact and isolated from

the surroundings. Evaluate the final temperature T f , supposing that TA TB .

7- What is the quantity of heat required to rise the temperature of one mole of CO2 between

300 and 400 K ? Use the data proposed above in chapter V.

8- right, wrong, why ?

a) During an adiabatic transformation, temperature remains constant since the system does

not exchange heat with the surroundings.

b) A process is isothermal if no heat is exchanged between the system and the surroundings.

c) Reversible an irreversible adiabatic expansion of an ideal gas is associated to a decrease of

its internal energy.

d) isothermal compression of an ideal gas is associated to an increase of its internal energy.

9- What is the supplied work to decrease the volume of 2 moles of an ideal gas in the STP of

75% at constant temperature. What is the heat exchanged with the surroundings. Precise the

direction of the transfer.

10- 50 L of ideal gas is embedded under a pressure of 2 atm in a cylinder closed by a piston.

The piston is unlocked and the gas abruptly expands, then after a while the system is again at

thermodynamic equilibrium, at a final temperature identical to the initial one. Calculate the

exchanged work and heat with the surroundings.

11- From the definition of an adiabatic process, establish the equation relating P and

V during a reversible adiabatic process. Deduce the equation relating P and T .

12- Calculate the ratio of the slopes in the Clapeyron diagram of an isotherm and the

adiabatic at the same point ( P, V ) .

13- 1 mole of an ideal gas in the CNTP is submitted to an adiabatic expansion down toa

pressure of 0.5 atm. Calculate :

11/28

- the work of the gas,

- the final temperature,

- the internal energy variation.

C Thermochimistry

14- An athermal reaction :

a) is used to product heat

15- The heat of reaction of process leading a system from a state A to a state B is defined for

a process A B

a) isochoric

b) monothermal ( TA TB )

c) isobaric

d) isothermal

16- The heat transferred to a close system during a chemical reaction processed at constant

pressure (or constant volume) is equal to the enthalpy variation (internal energy) of the

system.

17- Calculate r H 298 rU 298 for the following reactions and sort them out :

a) C6H6(l) C6H6(g)

b) Fe2O3 (s) + 3 CO(g) 2 Fe(s) + 3 CO2(g)

c) (NH4)2SO4(s) 2 NH3(g) + H2O(g) + SO3(g)

d) C2H4(g) + 3 O2(g) 2 CO2(g) + 2 H2O(l)

a) a unique state defined at T 298 K and Po 1 atm

b) a unique state defined at T 298 K and Po 1 bar

c) a state defined for a temperature T under the pressure of 1 bar.

c) a state defined for a temperature T under the pressure of 1 atm.

a) always the ideal gas state at temperature T under the pressure of 1 bar,

b) generally the physical state of the most stable simple compound at temperature T under the

pressure of 1 bar.

20- from :

N2O3(g) NO(g) + NO2(g)

2 NO2(g) N2O4(g) (2)

(1)

rH298(2) = - 57,2 kJ.mol-1

12/28

21- Between the different possibilities, which one is the standard formation enthalpy of

copper sulfate ?

Cu2+(sol) + SO42-(sol) CuSO4(s)

Cu(s) + SO2 (g) + O2(g) CuSO4(s)

Cu(s) + S(s, orthorh) + 2 O2(g) CuSO4(s)

Cu (s) + S(s, orthorh) + 4 O(g) CuSO4(s)

Does it mean that copper sulfate is prepared from this reaction ?

22- Calculate the heat of combustion in excess of oxygen of Al(s), C(s, graphite), H2(g),

CH4(g) et CH3OH(l), supposing the produced water liquid. Consider the isobaric reaction heat

to be equal to the standard reaction enthalpy. Use the data table in the exercise book.

(a) The latent heat corresponding to the physical state transformation of a substance is the

molar enthalpy variation during the transition.

(b) Depending on the substance, fusion is either endo- or exothermic.

(c) Fusion and sublimation are always endothermic.

(d) Crystallisation may be exothermic.

(e) Fusion, vaporisation and sublimation are always endothermic.

(f) Latent heats are independent of the temperature.

13/28

answers

Q energie

T

T

1 [CP] or [CV]

mL t -2

energie

force

Q

=pression A ; Pascal ; intensive (since V is

mL2 t -2 L-3 =

2

surface

V

V

L

extensive)

Q energie mL2 t -2 3

=

=L =volume ; m3 ; extensive (since P isintensive).

h

-1 -2

P

P

mL t

b) give and T their value for the ideal gas.

c) C P CV

8.32 J.mol-1K-1.

idal gas

V water 18cm3 ; C P CV

V Al 1 cm3 ; C P CV

4, 6.10

water

1.3310

10

Al

11

= 0.67 J.mol-1K-1.

= 0.011 J.mol-1K-1.

Conclusion : quantitatively, C P and CV are closer when the state is more condensed and the

substance of low compressibility.

3a) The volume variation being low and Q equivalent to an elementary variation, Q, one can

write Q = V = P V = 1.013.105 .(- 10-5) = - 1.013 J.

b)

can

Qrev nRT1 ln

not

Vf

Vi

be

considered

8.32 273ln

constant

( = P)

and

must

be

integrated.

11.4

= -1343 J.

22.4

c) For this intermediary case the approximated calculation leads 101,3 J, while the more

exact one 103,7J. The approximation remains correct until few percents.

Q = hP = - V P = - 22.4.10-3 . 10 = - 0.224 J.

b)

can

Qrev nRT1 ln

not

Pi

considered

8.32 273ln

Pf

CP CV

be

14/28

TV 2

constant

(h = -V)

and

must

be

integrated.

1.013

= - 911 J.

1.513

h

V T h V T TV

water =

= 1.55 108 Pa

10

4, 6 10

being low)

-b) Q = h P = -1.29 10-6.5 104 = -0.0645 J. (Same remarks, the compressibility of the liquid

being weak, V can be considered constant).

6- Heat quantity supplied by the hot block = heat quantity received by the cold block

mA

m

C PA TA T f B C PB T f TB

MA

MB

mA

m

C PATA B C PBTB

M

MB

Tf A

mA

m

C PA B C PB

MA

MB

400

Q=

44.1dT 9.03103TdT

300

8.53105

dT

T2

(400) 2 (300) 2

1

1

8.53105

= 4015 J.

2

400 300

8 - a) wrong

b) wrong

(isothermal)

9 Wrev nRT ln

Vi

Vf

d) wrong U = 0

15/28

P

V f Vi i

Pf

1/

= 36.75 L

1

1

( Pf V f PV

(0.5 36.75 22.4) 102 - 1006 J

i i)

0.4

1

W C v (T f Ti )

or PfVf = R Tf

Tf 221 K

C) - Thermochimistry

14 c)

15 b)

16 yes

17 c>a>b>d (compare ng)

20: -22.0 kJ.mol-1

21: the third, no.

22- 31.05 ; - 32.76 ; - 141.8 ; - 55.50 ; - 22.7 (heat supplied to the surroundings)

16/28

Chapter VI

The second law

1. Consider a boat near the tropics. It transfers heat from the warm sea water which is directly

transformed into mechanical energy for the boat motion and it rejects ice to the sea. Is it

possible ?

2. A system (ideal gas) follows a Carnot's cycle (two adiabatic and two isothermal

processes) and supplies a work of 300 J. The reservoir temperatures are respectively

T1 450 K and T2 300 K . Calculate the heat quantities Q1 and Q2 exchanged between the

system and the reservoirs, give their sign. Calculate the energy fraction transformed to work.

3. A system

equilibrium state B through two different processes, one reversible and the other one

irreversible. we can write :

a) S irr S rev

b) S irr S rev

c) S irr S rev

d) none of these answers. We must describe both processes to decide.

a) the energy conservation,

b) the entropy conservation,

c) the disorder conservation,

d) the irreversible evolution of the universe to an increasing state of disorder,

e) the irreversible evolution of a system to an increasing state of disorder.

5. Right or wrong ? For any process, the second law requires the entropy variation of a system

to be : a) positive or nil,

c) positive,

b) negative or nil,

d) No requirement is imposed by the second law to a system.

17/28

a) is a state function,

b) is an intensive quantity,

c) of the universe can be created but not destroyed,

d) of a system can vary only if there is energy transfer to the surroundings,

e) of an isolated system is constant,

f) of a pure substance at a unique microscopic configuration is nil at 0K.

7. Right or wrong ?

a) Consider a thermal reservoir at temperature T , supplying the heat quantity Q to a system.

Its entropy variation is Q / T , whatever the conditions (reversible or irreversible) of heat

transfer.

b) A reversible work transfer does not lead to entropy variation.

c) A heat quantity of 300 J is transferred from a reservoir at 300 K to a system at the same

temperature. What is the entropy variation of the system ?

8. 100 g of water is heated from 25C to 80C, calculate the entropy variation.

9. The vaporisation of water at 100C under a pressure of 1 atmosphere is a ------------process. Calculate the entropy variation of 1 mole of water evaporating in these conditions

0

2300 kJ kg -1 ).

(The corresponding enthalpy is H H 398

10. Two identical solids of identical heat capacities 100 JK -1 at initial temperatures of

T1 700 K and T2 300 K respectively are connected. We suppose that they are perfectly

isolated from the surroundings. Describe the final equilibrium state, calculate the entropy

variation between the two states and comment on it.

a) the internal energy remains constant,

b) there is no heat transfer owing to the isothermal nature of the process,

c) the entropy of the surroundings remains constant,

d) the gas entropy increases,

e) the entropy of the universe remains constant.

18/28

12. Calculate the entropy variation of one mole of ideal gas submitted to a reversible

isothermal compression from 1 atm to 3 atm at 25C.

a) at constant internal energy,

b) at constant enthalpy,

c) at constant entropy,

d) none of these answers.

a) The heat transferred to the surroundings in the case of an irreversible adiabatic process is

not nil, contrary to the reversible case, but it is low.

b) The entropy variation of the system is negative and that of the surroundings positive.

c) The entropy variation of the system is positive and that of the surroundings negative.

d) none of these answers because ----------------.

19/28

Answers

1. no

2. Q1 900 J , Q2 600 J .

3. a)

4. only d) is true

5. d) true.

6. a), c) and f) true

7. a), b) true c) S 10 JK -1

8. S 70.8 JK -1

9. reversible - S 0.111 JK -1 .

10. at equilibrium T1 T2 500 K , S 17.44 JK -1

11. a), d) e) true

12. S 9.14 JK -1

13. d)

14. d)

20/28

Chapter VII

Application of the two laws

1- Consider an elementary process of a system of state equation f ( P, V , T ) 0 . How many

possible expressions of the heat quantity Qrev transferred to the surroundings can be

written ? Detail these expressions and the definition of the corresponding calorimetric

coefficients.

Consider a system of state equation f ( P, V , T ) 0 ,

U

a) CV

T V

U

b) h

P T

P

c) T

T V

V

d) h T

P T

3- Right or wrong ?

a) The COPrev of a heat engine only depends on the high and low temperatures of the

reservoirs.

b) The COPrev of a heat pump is lower than unity,

c) The COPrev of a frigorific machine is higher than unity,

d) "COP" and efficiency are equivalent.

4- Calculate the reversible efficiency of a heat machine working with two reservoirs at

temperature 300 K and 500 K?

5- Energy is transferred to a flat by a heat pump with an efficiency of 12. The temperature in

the flat is 20C and the behaviour is reversible. What is the temperature of the low

temperature reservoir ?

6- An engineer pretends having designed a heat engine working between 200C and 50C

with a COP of 0.35. Is this value :

a) normal,

c) good,

d) excellent ?

e) impossible.

21/28

22/28

Answers

1- three different expressions (two independent variables). see lecture for the two expression

in terms of dT , dP or dT , dV .

H

V

2- a) right; b) wrong h

V ; c) right; d) wrong h T

P T

T P

4- 0.4

5- -4.4C

6- d) COPrev 0.37

23/28

Chapter IX

thermodynamics of pure substances

application to phase change

simple tests

1 - right or wrong ?

a) The Gibbs free energy of a system is a state function,

b) it is written G H TS ,

c) for an elementary process : dG SdT PdV ,

d) if F is the Helmoltz free energy of the system G F PV

a) The Gibbs free energy is thermodynamic potential because it can predict the evolution of a

system for any process.

b) During a reversible process at constant pressure and temperature, the Gibbs free energy of

a system does not vary.

c) During a process at constant pressure and temperature, the Gibbs free energy of a system

always remains constant.

d) The Gibbs free energy variation G A B of a system between the states A and B is

minimum for a reversible process A B .

e) A spontaneous evolution of a system at constant temperature and pressure always implies a

decrease of the Gibbs free energy.

3 - complete

The molar latent heat of vaporisation of a substance is the heat quantity required to transform

one mole of this substance from the -------- state to the -------- state, at constant -------- and ------. This explains on one hand the terms of ------- heat and on the other hand that this

transferred heat corresponds to an -------- variation of the system constituted of one mole of

the substance. This also explains the equivalent name of molar vaporisation ---------- .

4 - terms

a) Name the transformation solid gas, gas liquid, solid liquid and their opposite.

b) What is a supercritical fluid ?

24/28

d) define the "critical point".

6- at 0C, the saturation vapour pressure of CO2 is 34 atm. In these conditions, the molar

volume of liquid and gas CO2 are respectively 45 and 450 cm3. Still under theses conditions

the volume one mole of CO2 is 200 cm3. Calculate the molar ratios of the liquid and the solid.

(a)

dP S S

dT V V

(b)

the

molar

sublimation

of

NH3

is

31.29 kJmol-1,

and

its

enthalpy

molar

vaporisation

Calculate

the

molar

solidification enthalpy.

diagram

H

dP

dT T V V

(c) ln P

trs H

Cte

RT

25/28

Answers

1- a) true, b) wrong, c) wrong, d) true

2- a) wrong, b) true, c) wrong (only true for a reversible process), d) wrong G is a state

function, e) true

3- The molar latent heat of vaporisation of a substance is the heat quantity required to

transform one mole of this substance from the liquid state to the vapour state , at constant

pressure and temperature. This explains on one hand the terms of latent heat and on the other

hand that this transferred heat corresponds to an enthalpy variation of the system constituted

of one mole of the substance. This also explains the equivalent name of molar vaporisation

enthalpy.

4- cf course

5-

P

supercritical fluid

liquid

critical point

vapour +liquid

boiling curve

6- lever rule : xv

200 45

0.383

450 45

vapour

dew curve

T6

T1

T

xl 1 xv 0.617

7- cf course

8- a) and b) always true, c) only true for the equilibrium curve between a condense phase and

vapour, considered as an ideal gas, if the volume of the condense phase is neglected and

H independent of temperature.

9- sol H ( NH 3 ) 5.61 kJmol1

10- see course

26/28

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