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:

i and i' are the stoechiometric coefficients of reactants and reaction products
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 0 Equations (1) and (2) give H , 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
f 0 be known. This is why another parameter, heat (enthalpy) of formation, H , 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 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 60C = 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:
m1 c H O ( t 2 t1 ) = m 2 c H O ( t 3 t1 ) + C c ( t 3 t1 )
2 2

(3)

(4)

m1 and m2 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: 2

( Na

+ OH ) + ( H + + Cl ) = ( Na + + Cl ) + H 2 O

(5)

2( Na + + OH ) + 2 H + + SO4

) = ( 2 Na (
+

+ SO4

) + 2H O
2

(6) (7)

( NH

+ 4

+ OH + ( H + + Cl ) = NH 4 + Cl + H 2 O

INSTRUCTIONS 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 = ( C c + mR c R ) (t f t i )

(8)

where m R c R is the sum of the masses of the acid and base solutions.
m R c R = m a c a + mb cb Q = ( c cal + m a c a + mb c b ) t

where, ma, mb - represent the acid (a) or base (b) solution mass; ca, cb - reprezint cldura specific a soluiilor de acid i de baz. m acid = V acid acid ; [ g ]
acid = baz = 1,06 [ g / cm ]
3

mbaz = Vbaz baz ; [ g ] c a = c b = 3,9 [ J / g grad ]

Ccal = ? [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 O
2

(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 50 mL sol. NaOH .....n moli NaOH 1000 mL sol. NaOH....0.5 moli NaOH

n = 0,025 moli HCl = 0,025 moli NaOH Results interpretation: It will be established the endothermic or exothermal nature of the studied process. The thermal effects of the reactions 5, 6 and 7 will be compared

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 thermometer. After 3 mintutes the initial temparature is measured (ti); At the analytical balance 2g of NH4Cl are weighted and then are introduced in the water from the 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 ) t

where, csol = 4.18 [J/grad] represent the caloric capacity of the solution, ccal= ? [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 + (3 16)= 101 [g/mol] n= m ; M n = 2/101 0,02 moli.
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 3. APPLICATION OF HESSS LAW The enthalpy of formation of ammonium sulfate can be calculated by means of the thermal effect of the following reaction: 2 NH 3 ( g ) + H 2 SO4 ( l ) ( NH 4 ) 2 SO4 ( s )
r H x

and the heats of formation of the reactants. The heats of formation of ammonia and sulfuric acid have
f 0 g the following values: H ( NH 3 ) = 11kcal / mol , l f H 0 ( H 2 SO4 ) = 193.19kcal / mol

The heat of reaction can be obtained from the thermal effects of the following processes: 1. 2. 3. 4. NH 3 ( g ) + nH 2 O( l ) NH 4 OH ( sol ) H 2 SO4 ( l ) + nH 2 O( l ) H 2 SO4 ( sol ) H 2 SO4 ( sol ) + 2 NH 4 OH ( sol ) ( NH 4 ) 2 SO4 ( sol ) ( NH 4 ) 2 SO4 ( s ) + nH 2 O( l ) ( NH 4 ) 2 SO4 ( sol )
r H 1 = 8350cal / mol r H 2 = ? r H 3 = ? r H 4 = ?

It is easy to observe that our reaction of interest may be obtained by a linear combination of reactions 1, 2, 3 and 4, so that its thermal effect is calculated by the corresponding summation of the heats of processes 1-4:
r H x = 2r H 1 + r H 2 + r H 3 r H 4

(1)

The thermal effects of processes 2-4 have to be measured. 5

EXPERIMENTAL In a calorimeter as that described before, 50 mL of distilled water are introduced and the initial temperature is measured (t1). 1 mL of concentrated sulfuric acid is mixed with the water from the calorimeter and the constant value of the final temperature is registered (t2). 5 mL of concentrated ammonia solution are poured in the calorimeter and a new stable value of temperature is read (t3). The solution is thrown and again, 50 mL of distilled water are put inside the calorimeter. The initial temperature is read (t4) and then 5 g of (NH4)2SO4 are dissolved in it. When the dissolution process has ended, the final temperature (t5) is registered. RESULTS AND CALCULUS The molar thermal effects are calculated by means of the following equation: H i =

( C c + msol c sol ) T
ni

C c - calorimeter constant was measured before. The density and specific heat solutions are assimilated with those of water ( = 1000 g / L, c = 1 cal / g K ) ni - the mole number of consumed reactant for process 2 and 3: n H 2 SO4 = and n ( NH V H 2 SO4 H 2 SO4 c H 2 SO4 M H 2 SO4
)
SO4

; c H 2 SO4 = 94%; H 2 SO4 = 1,83 g / cm 3

4 2

m( NH

4 2

SO4 SO4

M ( NH

4 2

, for process 4.
)
SO4

f 0 The results for r H i are introduced in equation (1) and H ( NH

4 2

is calculated:
(3)

f H 0 ( NH

4 2

SO4

= f H 0 ( NH 3g ) + f H 0 ( H 2 SO4l ) + r H x