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CHEMICAL THERMODYNAMICS

Chemical reactions involve either heat evolution (exothermic) or absorption (endothermic). The heats of reaction are measured either at constant pressure or constant volume, and they are expressed as differences in enthalpy or internal energy, respectively. In thermochemical tables, the thermal effects of reactions are usually found as enthalpy changes (at constant pressure of 1 atm). For general reaction as:
1 A1 + 2 A2 + ... + i Ai + ... 1' A1' + 2' A2' + ... + i' Ai' +

(1)

The standard heat of reaction at constant pressure is easily found from the thermal balance:
H r0 = i' H i' i H i

(2)

where:

and i' are the stoechiometric coefficients of reactants and reaction products i
respectively,
H i and H i' are the corresponding molar enthalpies
Ai and Ai' designate the participants in the reaction and reactions products, respectively
r H 0

Equations (1) and (2) give

, which is the molar heat of reaction. The heat of reaction is an

extensive quantity; it depends on the amount of reacting substances. Because the internal energy includes the kinetic and interaction energies of all particles of the system, its absolute value as well as that of enthalpy cannot be known. Only changes in their values can be known. This is why another parameter, heat (enthalpy) of formation,
f H 0

, was introduced in the

equation of the heat reaction at the place of absolute values of enthalpy. The enthalpy of formation is the thermal effect associated with the reaction by which a compound is obtained from elements in their stable state (as a consequence of this, the heat of formation of elements is zero).

r H 0 = i' f H i'0 i f H i0
i' i

(2)

The heats of reaction obey the laws of thermochemistry, which are consequences of the property of total differential of dH (and dU ). One of them the Hess law states that the heat of reaction does not depend on the path of the process (chemical reaction), bur only on the limiting states initial and

final. This law makes possible the calculation of the thermal effect of a reaction, by summing the thermal effects of reactions involving the same participants, if the former reaction may be expressed as a linear combination of the latter ones. The heat of reaction can be measured experimentally by calorimetry. The classical equation (3) can be used:
Q =C t

(3)

C the heat capacity of the system consists of two parts: the heat capacity of the calorimeter C c (calorimetric vessel, thermometer, stirrer) and that of the reacting system C R . The first term is known as the calorimetric constant, the second one may be calculated as the product of the specific heat and the mass of the reacting system. Equation (3) becomes:
Q = (C c + m R c R ) t

(3)

1. DETERMINATION OF THE CALORIMETERS CONSTANT APPARATUS: calorimeter, calorimetric vessel (beaker), thermometer, stirrer, beaker for heating, water, heating device (electrical or Bunsen burner) . INSTRUCTIONS: Put 50 mL of water in the calorimetric vessel and record its temperature t1 . Put another 50 mL of water in a beaker and heat it up to 60 C = t 2 . Put the warm water in the calorimetric vessel, stir its content and notice the temperature each minute until a constant value is observed ( t 3 ). Calculate calorimeters constant using the thermal balance equation: (4) m1 c H O ( t 2 t1 ) = m 2 c H O ( t 3 t1 ) + C c ( t 3 t1 )
2 2

m1 and m 2 are the masses of warm and cold water respectively.

2. MEASUREMENT OF THE HEAT OF NEUTRALIZATION The heat of neutralization of a strong acid with a strong base is the heat evolved in the formation of one mole of water from its ions. Consequently it has a constant value of -57.3 kJ/mol irrespective of the strong acid and base. When at least one of the two reactants is a weak electrolyte, the heat of neutralization is smaller, because a certain amount of energy is used for its dissociation. In this work, the thermal effect of the following reactions will be determined:

( Na

+ OH + H + + Cl

) (

)
2

( Na

+ Cl + H 2 O
+

(5) (6

2 Na + + OH + 2 H + + SO4

) (

( 2Na

+ SO4 + 2 H 2 O

( NH
INSTRUCTIONS

+ 4

+ OH + H + + Cl

) (

( NH

+ 4

+ Cl + H 2 O

(7)

Put 50 mL of solution NaOH 0.5M in the calorimetric vessel and record its initial temperature (ti). Add 25 mL of HCl solution at same temperature (room temperature). Stir and record the final temperature ( t f ), the temperature which remains constant during 1 min. The same will be done for reactions (6) and (7). RESULTS AND CALCULUS Fill the following table:
No. 1 2 3 Chemical reaction HCl + NaOH NaCl+ H2O H2SO4+2NaOHNa2SO4+ 2H2O HCl + NH4OH NH4Cl + H2O ti [C] tf [C] Q [J] H [J/mol] H [kcal/mol]

The evolved heat is calculated as:


Q = ( Cc + m R c R ) (t f t i )

m R c R = m a c a + mb cb Q = ( C cal + ma c a + mb cb ) t

(8)

Where: m R is the sum of the masses of the acid (ma) and base (mb) solutions. ca, cb - represents the specific heat of the acid and base solutions
m acid

acid

The density and the specific heat of the solutions are approximated to those of water. = V acid acid ; [ g ] mbaz = Vbaz baz ; [ g ] 3 = baz = 1,06 [ g / cm ] c a = c b = 3,9 [ J / g grad ]

Ccal = 85 [J/grad] The heat of neutralization is calculated by dividing the heat Q through the mole number of water

formed from its ions:


n H = Q nH
2O

(9)

The sign is changed because exothermic effects are considered negative by convention. The moles number of acid and base is: 25 mL sol. HCl......n moli HCl 1000 mL sol. HCl......1 mol HCl Results interpretation: It will be established the endothermic or exothermal nature of the studied process. Compare the thermal effects of the reactions 5 with 6 and 5 with 7. 50 mL sol. NaOH .....n moli NaOH 1000 mL sol. NaOH....0.5 moli NaOH

n = 0,025 moli HCl = 0,025 moli NaOH

3. MEASUREMENT OF THE HEAT OF DISSOLVING SUBSTANCES: NH4Cl (amonium chloride) and NaNO3 (sodium nitrate) in solid state.
INSTRUCTIONS Put inside the calorimeter 100 mL of distilled water, measured with graduated cylinder, and a At the analytical balance 2g of NH4Cl are weighted and then are introduced in the water from the

thermometer. After 3 mintutes the initial temparature is measured (ti); calorimetric system. The temperature variation during the dissolving process are observed. When all the salt is disolved, the temperature is constant and this temperature is recorded (tf). Similar procedure will be used for NaNO3. RESULTS AND CALCULUS Fill the following table: Salt NH4Cl NaNO3 m [g] 2 2 M [g/mol] n [mol] ti [oC] tf [oC] t [0C] Q [J] H [J/mol] H [cal/mo]

Calculate Q using the following relation:


Q = (C cal + c sol m sol ) t

where, csol = 4.18 [J/grad] represents the caloric capacity of the solution, Ccal= 85 [J/grad]

Calculate the moles numbers n of the dissolved substance dividing the substance mass to its molecular mass M. Example for KNO3 (potassium nitrate): AK = 39 [g/mol] AN = 14 [g/mol] AO = 16 [g/mol]
M KNO3 = 39 + 14 + (316)= 101 [g/mol]
n= m ; M

n = 2/101 0,02 mols.


Q n

d Calculate the dissolving enthalpy using the relation: H =

RESULTS INTERPRETATION: The endothermic or exothermal nature of the studied process will be established

Applications: 1. Write the following neutralization reactions, using ions: KOH + HNO3 LiOH + H2SO4 2. When neutralizing of 40 cm3HCl 1n with 60 cm3 NaOH 0.5N a difference of 2.5C was observed. Calculate the reaction enthalpy if Cc = 100 cal/K 3. Calculate the volume of HNO3 that must be introduced in the calorimeter, knowing that it were used 60 ml NaOH, Cc = 100cal/grd and H = -13.5 kcal/mol