JP3138724B2 - Reaction analysis method and equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for collecting data by means of thermal analysis and analyzing a reaction occurring in a sample by processing the collected data.

[0002] Thermal analysis means generally means means for measuring the physical properties of a sample or the physical properties of a product produced by a reaction of a sample while changing the temperature of the sample according to a predetermined program. Say. The physical properties include mass, temperature, enthalpy, dimensions, mechanical properties, acoustic, optical, electrical, and magnetic properties. In addition, reaction analysis by this means is used for elucidation and prediction of material generation reaction, evaluation of instability of unstable substances such as explosives, prediction of temporal change of materials such as electric materials under various environments, etc. There are various usage forms.

[0003]

2. Description of the Related Art Conventionally, in reaction analysis, a reaction mechanism is determined by observing a change in a sample at a constant temperature, a reaction rate constant is obtained, and the logarithm of the reaction rate constant is linear with respect to the reciprocal of absolute temperature. Using the relationship (Arrhenius's law)
The activation energy has been obtained from the gradient.

In recent years, however, with the development and widespread use of thermal analysis means for observing changes while increasing the temperature at a constant heating rate, a number of methods for analyzing reactions using this thermal analysis means have been proposed. (J. Flynn and LA Wall, J.
Res. Natl. Bur. Standard, 70A (1966) 487; Kotaro Kotaro, Ozawa Takeo eds., New edition thermal analysis (Kodansha, 1992). Among them, a method proposed by one of the present inventors (T. Ozaw
a, J. Thermal Anal., 2 (1970) 301) has an ASTM (American Soc.
Society for Testing Materials)
Widespread. This method utilizes the fact that the common logarithm of the heating rate and the reciprocal of the absolute temperature at the point where the rate of change is maximal have a linear relationship, and the gradient is 0.45670.4E / R (R is a gas constant). To determine the activation energy ΔE, and further analysis is proceeding. This method is incorporated in the apparatus as data processing software for a computer attached to the thermal analyzer. Further, Japanese Patent Application No. 3-72930 discloses that the natural logarithm of the maximum rate of change at a constant temperature rise is linearly related to the reciprocal of the absolute temperature, and that the gradient is ΔE / R. Have been.

[0005]

However, the above prior arts are all applied when the reaction proceeds according to a single elementary process (elementary reaction), and a complex reaction involving a plurality of elementary processes. (Hirotaro Kobe, Takeo Ozawa, Ed., New Edition Thermal Analysis (Kodansha, 199
2)).

Accordingly, an object of the present invention is to provide a method capable of analyzing a complex reaction involving a plurality of elementary processes. In particular, as described later, a plurality of reaction mechanisms are involved. It is an object of the present invention to provide a method capable of analyzing a parallel competition reaction and an apparatus therefor.

[0007]

The reaction analysis method of the present invention for achieving the above-mentioned object includes: 1) increasing the temperature of a sample, and 2) changing the physical properties of at least a part of the sample under the increased temperature. The rate or rate of change and the rate or rate of formation of the product resulting from the reaction of the sample are measured sequentially with temperature. 3) At a constant rate of change or rate of change of the sample, the rate of formation of a plurality of different products or 4) elucidate the reaction mechanism by comparing the formation rates or formation rates with each other, and determine the reaction rate from the relationship between the temperature and the formation rate or formation rate at a constant change rate or change rate of the sample. It consists of elucidating the activation energy, frequency factor, reaction order and the like.

An apparatus for performing an analysis using this method includes:
Heating means for heating the sample in different heating schemes, means for sequentially measuring the rate of change or the rate of change of at least a portion of the physical property of the sample under heating, and the formation of products produced by the reaction of the sample Means for sequentially measuring the rate or production rate;
A temperature measuring means for sequentially measuring the temperature during temperature increase, and a rate of change or a rate of change of a plurality of different products at a constant rate of change or rate of change of the sample, and And means for calculating the reaction activation energy, frequency factor, reaction order, and the like from the relationship between the production rate or production rate and the temperature.

The temperature of the sample is raised according to a predetermined program, and the rate of temperature rise can be changed by changing this program. The physical properties for which the rate of change is measured for the sample to be heated include mass, temperature, enthalpy, dimensions, mechanical properties, acoustic properties, optical properties, electrical properties, magnetic properties, etc., as described above. . The heating rate is changed by repeating the steps described in the above 1) and 2) with different programs for the same kind of sample, and the rate of change of the sample and the production rate of the product are measured for each heating rate. .

Using the data measured in this manner, first, the rates of formation of a plurality of different products at a constant rate of change of the sample are compared with each other, so that the reaction is a complex reaction involving a plurality of elementary processes. Make sure that In particular, it is confirmed that the reaction to be analyzed is a system to which the present invention can be applied, that is, a parallel competitive reaction involving a plurality of reaction mechanisms, according to the procedure described in detail in the section of operation.

FIG. 1 is a block diagram showing the principle configuration of the reaction analyzer of the present invention. In FIG. 1, a reaction analyzer of the present invention includes a heating device (10) capable of heating a sample (50) according to a plurality of different programs;
A change rate measuring means (1) for sequentially measuring a change rate or a change rate of at least a part of the physical property of the sample (50) under the elevated temperature.
2), means (14) for successively measuring the production rate or production rate of a plurality of different products produced by the reaction of the sample, temperature measuring means (16) for successively measuring the temperature during temperature increase, and Means (18) for comparing the production rates of the plurality of different products at the rate of change, and the activation energy, frequency factor, reaction order, and the like of the reaction are calculated from the correlation between the rate of change, the rate of production, and the temperature. Means (20).

[0012]

First, conditions to be satisfied by a system to which the present invention can be applied will be described below.

When a certain physical property of a reacting sample is x,

[0014]

(Equation 1)

That the following holds. Incidentally, k _i is the rate constant for reaction i th elementary processes proceed in parallel, t is the time. g _i (x) is x relating to the reaction of the i-th elementary process.
It represents a certain function indicating a change, for example, if the primary reaction x, a x ² if secondary reactions. Denoting the amount of the product of the i-th elementary process by y _i ,

[0016]

(Equation 2)

## EQU1 ##

For a given reaction, g for all i
_{If i} (x) = g (x), then it is a parallel reaction system in which reactions of the same reaction type proceed. Such systems are found in thermal degradation reactions that cause the aging of electrical insulating materials. Paloniemi (IEEE Trans. Elect. Insu
According to l., 7 (1972) 172; ibid., 16 (1981) 1), in this reaction, a thermal decomposition reaction, a hydrolysis reaction, and a thermal oxidative degradation reaction proceed in parallel. Since the relative humidity and the oxygen concentration are considered to be almost constant, both of the latter can be regarded as pseudo-first-order reactions like the former. Therefore, the above equations (1) and (2) can be applied.

At the time when the rate of change of the sample takes a certain predetermined value, x is also constant. In this case, since g _i (x) is constant and equal to g _j (x) in a system in which the reaction modes of the elementary process are the same, the following equation holds.

[0020]

(Equation 3)

Accordingly, the mutual ratio of the formation rates of different products measured at the same constant sample change rate (including the case of simultaneous measurement) is equal to the ratio of the reaction rate constants of the elementary processes.

If Arrhenius' law,

[0023]

(Equation 4)

If (A, ΔE, R, T
Are the frequency factor, activation energy, gas constant, and absolute temperature, respectively. ), The ratio of the rates of formation of different products measured at the same time is

[0025]

(Equation 5)

[0026]

(Equation 6)

Thus, a plot of the ratio of a series of simultaneously measured production rates to the reciprocal of the absolute temperature is a straight line, and the slope is a value obtained by dividing the difference between the activation energies of the two by the gas constant. . Further, the ratio of A _i to A _j is determined from the intercept. Further, the straight line of the equation (6) for each change rate is gathered into one straight line regardless of the value of x. Therefore, if the straight line obtained from equation (6) is a single straight line irrespective of x for any i and j, g _i (x) becomes g _j
It is found that the reaction mode of each elementary process is the same as (x). Furthermore, if the slope of the plot of equation (6) is zero, it can be said that the product is a product from the same elementary process.

If the reaction mode of the elementary process is different, that is, if g _i (x) and g _j (x) are different,

[0029]

(Equation 7)

[0030]

(Equation 8)

## EQU1 ## At this time, if x is equal, that is, at the time when the change rate of the sample takes a certain predetermined value, the first term on the right side of the equation (8) becomes a constant. Therefore, a plot of the ratio of a series of simultaneously measured production rates against the reciprocal of the absolute temperature results in a straight line, the slope of which is the difference between the activation energies of the two divided by the gas constant. Furthermore, the ratio of A _i g _i (x) and A _j g _j (x) is determined from the intercept. The plots similarly obtained for each of the different rates of sample change will be different straight lines, but the straight lines will be parallel to each other. A _i g _i (x) for x from the intercept
The change in the ratio of / A _j g _j (x) is shown.

If the above-mentioned relations concerning the ratio of the production rates and the logarithm thereof are found, it can be confirmed that the observed reaction is in accordance with the equation (1).

Then, in different heating programs, the logarithm of the series of production rates measured at several constant sample rates of change is plotted against the reciprocal of the absolute temperature. A linear relationship is obtained, and the activation energy is obtained from the gradient.

[0034]

(Equation 9)

[0035] While A _i g _i (x) is obtained from the addition section,
Since A _i is a constant, the relationship between x and g _i (x) is obtained at different sample change rates. Therefore, the specific contents of g _i (x) become clear, the order of reaction and the like are obtained, and the frequency factor A can be determined.

From equation (1), if g _i (x) are all equal when the temperature is raised at a constant speed φ,

[0037]

(Equation 10)

[0038]

[Equation 11]

## EQU1 ## ∫K _i dT, since determined only by temperature regardless of the Atsushi Nobori rate, perform different measurements of heating rate,
If (1 / φ) ∫dx / g (x) at a constant temperature is calculated,
They will be equal to each other.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS There are not many known typical examples according to the formula (1). Then, the result of applying this method to the measurement result theoretically created by calculation is shown. The measurement results obtained by the calculation include the frequency factor (A _i ), the value of the activation energy (ΔE _i ) and the function (g _i (x)) representing the reaction mode in Equations (1) and (2) in advance. And determined by the Runge-Kutta method. An application example is shown below.

Example 1 FIG. 2 shows a first-order reaction (g _i (x) = x) using values of the following frequency factors (A _i ) and activation energies (△ E _i ).
FIG. 5 is a diagram showing a temperature change of a ratio (rate of change) between the amount (X) of the reactant and the initial amount (X _o ) when the parallel reaction proceeds by the Runge-Kutta method (hereinafter, X,
Y ₁ , Y ₂ and their rate of change are shown in the figure divided by X _o ). In this case, the number of elementary processes is 2, and the reaction mode of each elementary process is the same.

A ₁ = 2 * 10 ¹¹ s ⁻¹ ΔE ₁ = 40 kcal.mol ⁻¹ A ₂ = 1 * 10 ¹⁹ s ⁻¹ ΔE ₂ = 60 kcal.mol ⁻¹ φ = 0.25 to 10 K. min ^-1 where φ is the heating rate.

FIGS. 3 and 4 show the above A _i and △, respectively.
It shows the temperature change of the rate of change (dYi / dt) of reaction product 1 (Y ₁ ) and reaction product 2 (Y ₂ ), obtained using E _i .

FIG. 5 shows the logarithm (ln ((dY ₁ / dt) / log) of the ratio of the production rates of the two reaction products measured simultaneously.
(DY ₂ / dt))) plotted against the reciprocal of the absolute temperature. Although a linear relationship was obtained, each straight line converges into one straight line regardless of the rate of change of the reactants and the heating rate φ. The activation energy difference (ΔE ₁ −ΔE ₂ ) of the reactions of the two elementary processes is determined from the gradient of the straight line, and the ratio of the frequency factor (A ₁ / A ₂ ) is determined from the intercept. The values of (A ₁ / A ₂ ) and (△ E _1- △ E ₂ ) thus obtained are as shown in Table 1 and almost coincide with the values given in advance.

FIGS. 6 and 7 show that when the rate of change of the reactant takes several predetermined constant values at different heating rates, the logarithm (ln (dY _i /
dt)) is plotted against the reciprocal of the absolute temperature. The plot shows that X / X ₀ = 0.1, 0.3, ₀ .
Performed for 5, 0.7 and 0.9. In this case as well, a linear relationship was obtained, but they did not converge on one straight line. FIG.
G ₁ (X) * A ₁ and g ₂ (X) * A ₂
△ E ₁ and △ E ₂ are obtained from the gradient. The relations between g ₁ (X) * A ₁ and g ₂ (X) * A ₂ and X thus obtained are shown in FIGS. 8 and 9, respectively, and a linear relation is obtained. By examining the relationship between A * g (X) and X in this manner, it can be seen that the parallel reaction of this example is a primary reaction. The activation energies obtained from the gradients of the straight lines in FIGS. 6 and 7 are as shown in Table 2, and almost coincided with the values given in advance.

[0046] Example 2 FIG. 10, using the same value of A _i and △ E _i as in Example 1, 0
FIG. 4 is a diagram showing a temperature change of a mass (X) of a reactant obtained when a parallel reaction of the next reaction (g _i (X) = 1) proceeds.

FIG. 11 shows the temperature change of the production rate (dY _i / dt) of each reaction product (Y _i ) obtained using the above A _i and ΔE _i .

FIG. 12 shows the logarithm (ln ((dY ₁ / dt)) of the ratio of the formation rates of two reaction products measured simultaneously.
/ (DY ₂ / dt))) is plotted against the reciprocal of the absolute temperature. Although a linear relationship was obtained, Example 1
As in the case of, each straight line converges into one straight line regardless of the rate of change and the rate of temperature rise φ. (A ₁ / A ₂ ) determined in this example
And the values of (ΔE ₁ −ΔE ₂ ) are as shown in Table 1 and almost coincided with the values given in advance.

FIG. 13 shows the logarithm (ln (dY _i / d) of the rate of formation of the reaction product when the rate of change of the reactant reaches several predetermined constant values at different heating rates.
t)) is plotted against the reciprocal of the absolute temperature. Although a linear relationship was obtained, different from Example 1, each straight line was collected into one straight line for each reaction product. From the intercept of the straight line in FIG. _{13 g i (X) * A} it is, than the slope △ E _i
Is required. The relations between g ₁ (X) * A ₁ and g ₂ (X) * A ₂ thus determined and X are shown in FIGS. 14 and 15, respectively. In this case, both reactions are 0-order reactions (g
₁ (X) = 1 and g ₂ (X) = 1). Further, the activation energies obtained from the gradients of the respective straight lines in FIG. 13 are as shown in Table 2, and substantially matched the values given in advance.

[0050] EXAMPLE 3 FIG. 16, using the same value of A _i and △ E _i of Example 1, the secondary reaction _{(g i (X) = X} * X) reaction when parallel reaction proceeds in It is the figure which calculated | required and showed the temperature change of the mass (X) of the substance.

[0051] Figure 17, Figure 18, the above A _i and △ each reaction product was determined using E _i (Y _i) speed production of (dY _i /
dt).

FIG. 19 shows the logarithm (ln ((dY ₁ / dt)) of the ratio of the formation rates of two reaction products measured simultaneously.
/ (DY ₂ / dt))) is plotted against the reciprocal of the absolute temperature. Although a linear relationship was obtained, in this case as well, each straight line converges into one straight line regardless of the rate of change of the reactants and the rate of temperature rise φ. Moreover, the straight lines obtained in Example 1 and Example 2 also matched the straight lines obtained in this example. That is, regardless of the reaction mode (0 to secondary reaction), each straight line is gathered into one straight line. This means that the reaction modes of the elementary processes are the same, and equations (5) and (6) are satisfied. It is shown that this analysis method can be applied to a parallel reaction system having the same reaction mode. I have. Obtained in this example (A ₁ / A ₂₎ and _{(△ E 1 - △ E 2} ) value of is as shown in Table 1, and substantially coincides with the previously given value.

FIG. 20 and FIG. 21 show the logarithm (ln (dY _i /) of the production rate of each reaction product when the rate of change of the reaction product reaches several predetermined constant values at different heating rates.
dt)) is plotted against the reciprocal of the absolute temperature. A linear relationship was obtained, but did not converge on one line. G ₁ (X) * A from the linear intercept of FIGS. 20 and 21
₁ and g ₂ (X) * A ₂ , ΔE ₁ and ΔE ₂ are obtained from the gradient. G ₁ (X) * A ₁ and g thus obtained
₂ (X) * A ₂ and the relationship between the X, respectively 22, 23
It was shown to. As a result, quadratic curves were obtained in each case. This is because both elementary processes are secondary reactions (g ₁ (X)
= X ² , g ₂ (X) = X ² ). In this way, A * g (X) and X
By examining the relationship with, the reaction mode of the elementary process of the parallel reaction when the reaction mode is the same can be determined. The activation energies determined from the gradients of the straight lines in FIGS. 20 and 21 are as shown in Table 2, and almost coincided with the values given in advance.

Embodiment 4 FIG. 24 is a diagram showing a difference between Embodiments 1 to 3 using values of the following frequency factor (A _i ) and activation energy (エ ネ ル ギ ー E _i ).
FIG. 3 is a diagram showing a temperature change of a reactant amount (X) when a parallel reaction of a primary reaction (g _i (X) = X) proceeds. In this case, the temperature at which the rate of change of X is maximum is about 1000K.
It is.

A ₁ = 400 s ⁻¹ ΔE ₁ = 30 kcal.mol ⁻¹ A ₂ = 1.18 * 10 ⁷ s ⁻¹ ΔE ₂ = 50 kcal.mol ⁻¹ φ = 0.25 to 10 K.min ⁻¹ FIG. 25 and FIG. 26 show the temperature change of the production rate (dY _i / dt) of each reaction product (Y _i ) obtained using the above A _i and ΔE _i .

FIG. 27 shows the logarithm (ln ((dY ₁ / dt)) of the ratio of the production rates of two reaction products measured simultaneously.
/ (DY ₂ / dt))) is plotted against the reciprocal of the absolute temperature. Although a linear relationship was obtained, in this case as well, each straight line converges on one straight line regardless of the rate of change and the temperature rise rate φ. (A ₁ /
The values of (A ₂ ) and (ΔE ₁ −ΔE ₂ ) are as shown in Table 1, and almost matched the values given in advance.

FIGS. 28 and 29 show the logarithm (ln (d (d)) of the rate of formation of the reaction product when the rate of change of the reactant at some different rate of temperature increase reaches some predetermined constant value.
Y _i / dt)) is plotted against the reciprocal of the absolute temperature. In this case also, a linear relationship was obtained, but they did not converge on one line. G ₁ (X) * A determined in this example
The relationship between ₁ and g ₂ (X) * A ₂ and X is shown in FIGS. 30 and 31, respectively, and a linear relationship is obtained. From this, it can be seen that each of the parallel reactions in this example is a primary reaction. Further, the activation energies obtained from the gradients of the straight lines in FIGS. 28 and 29 are as shown in Table 2, and almost coincided with the values given in advance. Thus, it can be seen that the analysis method of the present invention can be applied to parallel reactions having the same reaction mode even when values of the activation factor and the frequency factor different from those in Examples 1 to 3 are used.

Example 5 FIG. 32 shows a primary reaction (g) using the same frequency factor (A _i ) and activation energy (△ E _i ) values as in Examples 1 to 3.
FIG. 2 is a diagram showing a temperature change of a mass (X) of a reactant when a parallel reaction between ₁ (X) = X) and a secondary reaction (g ₂ (X) = x ² ) proceeds. In this case, different from Examples 1 to 4, the reaction orders of the two types of elementary processes are different.

FIGS. 33 and 34 show the production rates (dY _i / d) of the respective reaction products (Y _i ) obtained using the above-mentioned A _i and ΔE _i.
t) is a temperature change.

FIG. 35 shows the logarithm (ln ((dY ₁ / dt)) of the ratio of the formation rates of two reaction products measured simultaneously.
/ (DY ₂ / dt))) is plotted against the reciprocal of the absolute temperature. Since the reaction mode of the elementary process is different (g ₁ (X) ≠ g ₂ (X)), a different straight line is obtained for each change rate, but the gradient is equal.

FIG. 36 and FIG. 37 show the logarithm (ln (dY _i /) of the production rate of each reaction product when the rate of change of the reaction product reaches several predetermined constant values at different heating rates.
dt)) is plotted against the reciprocal of the absolute temperature. In this case as well, a linear relationship was obtained, but they did not converge on one line. G ₁ (X) * A determined by the method of this embodiment
38 and 39 show the relationship between ₁ and g ₂ (X) * A ₂ and X, respectively. In this example, it can be seen that the reaction of reaction product 1 is a primary reaction and the reaction of reaction product 2 is a secondary reaction. Further, the activation energies obtained from the gradients of the straight lines in FIGS. 36 and 37 are as shown in Table 2, and almost coincided with the values given in advance. Thus, it can be seen that, unlike Examples 1 to 4, the analysis method of the present invention can be applied to a parallel reaction in which the reaction mode of each elementary process is different.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

According to the present invention, it has become possible to analyze the result of thermal analysis of a parallel reaction, which was impossible in the past.

[Brief description of the drawings]

FIG. 1 is a diagram showing the principle of the present invention.

FIG. 2 shows the temperature change of the ratio between the amount (X) of the reactant and the initial amount (Xo) when the temperature is raised from 500 ° C. at a constant rate of 0.25 to 10 ° C./min in Example 1. FIG. Less than,
X, Y ₁ , Y ₂ and their production rates are shown in the figure, divided by Xo.

FIG. 3 is a diagram showing a temperature change of a reaction product generation rate (dY ₁ / dt) when the temperature is raised at a constant speed from 500 ° C. at a rate of 0.25 to 10 ° C./min.

FIG. 4 is a diagram showing a temperature change of a reaction product generation rate (dY ₂ / dt) when the temperature is raised at a constant speed from 500 ° C. at a rate of 0.25 to 10 ° C./min.

FIG. 5 shows the logarithm (ln ((dY ₁ / dt) / (dY ₂ / d)) of the ratio of the formation rates of two reaction products measured simultaneously.
FIG. 7 is a diagram in which t))) is plotted against the reciprocal of the absolute temperature.

FIG. 6 shows the logarithm (ln (d (d)) of the production rate of each reaction product when the reaction rate of the reaction product becomes a constant value at different heating rates.
Y ₁ / dt)) is plotted against the reciprocal of the absolute temperature.

FIG. 7 shows the logarithm (ln (d (d)) of the formation rate of each reaction product when the reaction rate of the reaction product becomes constant at different heating rates.
Y ₂ / dt)) is plotted against the reciprocal of the absolute temperature.

FIG. 8 is a diagram showing a relationship between g ₁ (X) * A ₁ and X.

FIG. 9 is a diagram showing the relationship between g ₂ (X) * A ₂ and X.

FIG. 10 is a graph showing a temperature range from 500 ° C. to 0.25 to 10 ° C. /
FIG. 6 is a diagram showing a change in temperature of a reactant amount (X) when the temperature is increased at a constant speed in minutes.

FIG. 11 is a diagram showing a temperature change of a production rate (dY _i / dt) of a reaction product when the temperature is raised at a constant speed from 500 ° C. at a rate of 0.25 to 10 ° C./min.

FIG. 12 shows the logarithm (ln ((dY ₁ / dt) / (dY ₂ / d)) of the ratio of the formation rates of two reaction products measured simultaneously.
FIG. 7 is a diagram in which t))) is plotted against the reciprocal of the absolute temperature.

FIG. 13 shows the logarithm (ln) of the production rate of each reaction product when the reaction rate of the reaction product becomes constant at different heating rates.
(DY _i / dt)) is plotted against the reciprocal of the absolute temperature.

FIG. 14 is a diagram showing a relationship between g ₁ (X) * A ₁ and X.

FIG. 15 is a diagram showing a relationship between g ₂ (X) * A ₂ and X.

FIG. 16 is a graph showing the temperature in the range of 500 ° C. to 0.25 to 10 ° C. /
FIG. 6 is a diagram showing a change in temperature of a reactant amount (X) when the temperature is increased at a constant speed in minutes.

FIG. 17 is a diagram showing a temperature change of a production rate (dY ₁ / dt) of a reaction product when the temperature is raised at a constant rate from 500 ° C. at a rate of 0.25 to 10 ° C./min.

FIG. 18 is a diagram showing a temperature change of a production rate (dY ₂ / dt) of a reaction product when the temperature is increased at a constant rate of 0.25 to 10 ° C./min from 500 ° C.

FIG. 19 shows the logarithm (ln ((dY ₁ / dt) / (dY ₂ / d) of the ratio of the formation rates of two reaction products measured simultaneously.
FIG. 7 is a diagram in which t))) is plotted against the reciprocal of the absolute temperature.

FIG. 20 shows the logarithm (ln) of the production rate of each reaction product when the reaction rate of the reaction product becomes constant at different heating rates.
(DY ₁ / dt)) is plotted against the reciprocal of the absolute temperature.

FIG. 21 shows the logarithm (ln) of the production rate of each reaction product when the reaction rate of the reaction product becomes constant at different heating rates.
(DY ₂ / dt)) plotted against the reciprocal of the absolute temperature.

FIG. 22 is a diagram showing the relationship between g ₁ (X) * A ₁ and X.

FIG. 23 is a diagram showing a relationship between g ₂ (X) * A ₂ and X.

FIG. 24 shows a graph of Example 4 from 500 ° C. to 0.25 to 10 ° C. /
FIG. 6 is a diagram showing a change in temperature of a reactant amount (X) when the temperature is increased at a constant speed in minutes.

FIG. 25 is a diagram showing a temperature change of a production rate (dY ₁ / dt) of a reaction product when a temperature is raised at a constant rate of 0.25 to 10 ° C./min from 500 ° C.

FIG. 26 is a diagram showing a temperature change of a production rate (dY ₂ / dt) of a reaction product when the temperature is increased at a constant rate of 0.25 to 10 ° C./min from 500 ° C.

FIG. 27 shows the logarithm (ln ((dY ₁ / dt) / (dY ₂ / d)) of the ratio of the formation rates of two reaction products measured simultaneously.
FIG. 7 is a diagram in which t))) is plotted against the reciprocal of the absolute temperature.

FIG. 28 shows the logarithm (ln) of the production rate of each reaction product when the reaction rate of the reactant becomes constant at different heating rates.
(DY ₁ / dt)) is plotted against the reciprocal of the absolute temperature.

FIG. 29 is a graph showing the logarithm (ln) of the production rate of each reaction product when the reaction rate of the reaction product becomes constant at different heating rates.
(DY ₂ / dt)) plotted against the reciprocal of the absolute temperature.

FIG. 30 is a diagram showing a relationship between g ₁ (X) * A ₁ and X.

FIG. 31 is a diagram showing a relationship between g ₂ (X) * A ₂ and X.

FIG. 32 shows that in Example 5, from 500 ° C. to 0.25 to 10 ° C. /
FIG. 6 is a diagram showing a change in temperature of a reactant amount (X) when the temperature is increased at a constant speed in minutes.

FIG. 33 is a graph showing a temperature change of a production rate (dY ₁ / dt) of a reaction product when the temperature is raised at a constant speed from 500 ° C. at a rate of 0.25 to 10 ° C./min.

FIG. 34 is a diagram showing a temperature change of a production rate (dY ₂ / dt) of a reaction product when the temperature is raised at a constant speed from 500 ° C. at a rate of 0.25 to 10 ° C./min.

FIG. 35 is a graph in which the logarithm (ln ((dY ₁ / dt) / (dY ₂ / dt))) of the ratio of two reaction products measured simultaneously is plotted against the reciprocal of the absolute temperature.

FIG. 36 shows the logarithm (ln) of the production rate of each reaction product when the reaction rate of the reaction product becomes constant at different heating rates.
(DY ₁ / dt)) is plotted against the reciprocal of the absolute temperature.

FIG. 37 shows the logarithm (ln
(DY ₂ / dt)) is plotted against the reciprocal of the absolute temperature.

FIG. 38 is a diagram showing the relationship between g ₁ (X) * A ₁ and X.

FIG. 39 is a diagram showing a relationship between g ₂ (X) * A ₂ and X.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Temperature rising means 12 Change rate measuring means 14 Generation rate measuring means 16 Temperature measuring means 18 Comparison means 20 Calculation means 50 Sample

Claims (2)

(57) [Claims] (1) increasing the temperature of a sample; (2) determining the rate of change or the rate of change in the physical properties of at least a portion of the sample at an elevated temperature; By successively measuring the temperature with the temperature; 3) determining the production rates or production rates of a plurality of different products at a constant rate or rate of change of the sample; 4) comparing the production rates or production rates with each other. Reaction analysis characterized by elucidating the reaction mechanism and elucidating the activation energy, frequency factor, reaction order, etc. of the reaction from the relationship between the temperature and the production rate or the production rate at a constant change rate or change rate of the sample. Law. 2. A heating means for heating a sample (50) in different heating methods, and means (12) for sequentially measuring a rate of change or a rate of change of at least a part of physical properties of the sample under the heating. A means (14) for sequentially measuring the rate or rate of formation of a product generated by the reaction of the sample; a temperature measuring means (16) for successively measuring the temperature during the heating; and a constant rate of change or change in the sample. The production rates or production rates of a plurality of different products are compared with each other in the rate, and further, from the relation between the production rate or the production rate at the constant change rate or the change rate and the temperature, the activation energy of the reaction, the frequency factor, A reaction analysis device comprising means (18, 20) for calculating a reaction order and the like.