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BIOENERGTICA

Dr. Juan Pablo Damin


rea Bioqumica
Facultad de Veterinaria

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BIOENERGTICA

Cmo saber si un proceso vital se produce


en forma espontnea (por s solo)?

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BIOENERGTICA
Definicin:
Es el anlisis cuantitativo de las transformaciones
y utilizacin de la energa en los sistemas biolgicos.

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BIOENERGTICA
Definicin:
Es el anlisis cuantitativo de las transformaciones
y utilizacin de la energa en los sistemas biolgicos.

Cmo obtienen energa los seres vivos?

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BIOENERGTICA
Definicin:
Es el anlisis cuantitativo de las transformaciones
y utilizacin de la energa en los sistemas biolgicos.

Cmo obtienen energa los seres vivos?


energa de la luz solar

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BIOENERGTICA
Definicin:
Es el anlisis cuantitativo de las transformaciones
y utilizacin de la energa en los sistemas biolgicos.

Cmo obtienen energa los seres vivos?


energa de la luz solar

energa qumica obtenida de compuestos orgnicos


(nutrientes).

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Clasificacin de los organismos vivos segn
la forma de obtener energa

Fottrofos
Obtienen energa
de la luz solar

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Clasificacin de los organismos vivos segn
la forma de obtener energa

C6H12O6
Ej. Glucosa

Comp. orgnicos
Fottrofos
Obtienen energa
de la luz solar

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Clasificacin de los organismos vivos segn
la forma de obtener energa

C6H12O6
Ej. Glucosa

Comp. orgnicos
Fottrofos Quimitrofos
Obtienen energa Utilizan la energa qumica obtenida
de la luz solar de compuestos orgnicos
(nutrientes).
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BIOENERGTICA
Definicin:
Es el anlisis cuantitativo de las transformaciones
y utilizacin de la energa en los sistemas biolgicos.

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BIOENERGTICA
Definicin:
Es el anlisis cuantitativo de las transformaciones
y utilizacin de la energa en los sistemas biolgicos.

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BIOENERGTICA
Definicin:
Es el anlisis cuantitativo de las transformaciones
y utilizacin de la energa en los sistemas biolgicos.

obedecen

Las Leyes de la termodinmica

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Cules son las condiciones bajo las
que se producen en forma espontnea
los procesos vitales?

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Las Leyes de la termodinmica

Primera ley
(principio de conservacin de la energa)

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Las Leyes de la termodinmica

Primera ley
(principio de conservacin de la energa)

La energa no puede crearse ni destruirse,


pero puede transformarse.

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Las Leyes de la termodinmica

Primera ley
(principio de conservacin de la energa)

La energa no puede crearse ni destruirse,


pero puede transformarse.

La Cantidad Total de Energa en el Universo


permanece CONSTANTE

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Universo = Sistema + Entorno

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Universo = Sistema + Entorno
Sistema: parte del universo que elegimos
estudiar; es el conjunto de materia que
est experimentando un proceso qumico
o fsico determinado.

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Universo = Sistema + Entorno
Sistema: parte del universo que elegimos
estudiar; es el conjunto de materia que
est experimentando un proceso qumico
o fsico determinado.

Entorno: es el resto del universo

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Universo = Sistema + Entorno
Sistemas:
Abierto:

Cerrado:

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Universo = Sistema + Entorno
Sistemas:
Abierto: intercambia Materia y Energa

Cerrado:

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Universo = Sistema + Entorno
Sistemas:
Abierto: intercambia Materia y Energa

Cerrado: No intercambia Materia y Energa

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Universo = Sistema + Entorno
Sistemas:
Abierto: intercambia Materia y Energa
Nutrientes Animal desechos (desorden)
generan trabajo
y calor

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Universo = Sistema + Entorno
Sistemas:
Abierto: intercambia Materia y Energa
Nutrientes Animal desechos (desorden)
SERES VIVOS
NUNCA ESTAN EN generan trabajo
EQUILIBRIO
y calor

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SERES VIVOS
NUNCA ESTAN EN EQUILIBRIO
TERMODINMICO

Porque son sistemas abiertos caracterizados por un continuo


intercambio de materia y energa con el ambiente

y esa lejana del equilibrio funciona como motor que


permite la organizacin del sistema. (Jantsch, 1980)

En la clula, el mantenimiento del estado estacionario dinmico le


cuesta mucha ENERGA. (Carlier MF, 1991).

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Los sistemas vivos se mantienen alejados del equilibrio termodinmico
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Estado estacionario dinmico: UN EJEMPLO

Alimentos GLU
(carbohidratos)

CO2
(deshecho)

[ glucosa] en sangre es constante


=
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Estado estacionario dinmico: UN EJEMPLO
Sangre
SNC
Msculo
Alimentos GLU
(carbohidratos)

CO2
(deshecho)
Depsito Grasa

Hgado

[ glucosa] en sangre es constante


=
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Se puede vivir, crecer y reproducirse
sin la capacidad de generar trabajo?

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Cules son las condiciones bajo las
que se producen en forma espontnea
los procesos vitales?

La primera ley de la termodinmica nos da esa informacin?

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Las Leyes de la termodinmica

Segunda ley: El Universo tiende hacia el


desorden mximo, tiende al caos!

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Las Leyes de la termodinmica

Segunda ley: El Universo tiende hacia el


desorden mximo, tiende al caos!
Los procesos espontneos tienden al desorden
global del universo.
El sistema se ordena a expensas del
entorno y por tanto del universo que se
desordena

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Las Leyes de la termodinmica

Segunda ley: El Universo tiende hacia el


desorden mximo, tiende al caos!
Los procesos espontneos tienden al desorden
global del universo.
El sistema se ordena a expensas del
entorno y por tanto del universo que se
desordena

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Las Leyes de la termodinmica

Segunda ley: El Universo tiende hacia el


desorden mximo, tiende al caos!
Los procesos espontneos tienden al desorden
global del universo.
El sistema se ordena a expensas del
entorno y por tanto del universo que se
desordena

El grado de desorden se mide como Entropa!

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Las Leyes de la termodinmica

Segunda ley: El Universo tiende hacia el


desorden mximo, tiende al caos!
Los procesos espontneos tienden al desorden
global del universo.
El sistema se ordena a expensas del
entorno y por tanto del universo que se
desordena

El grado de desorden se mide como Entropa!


Da un criterio para determinar si un proceso es espontneo
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La energa Trabajo
de Se transforma en Calor
nutrientes Desorden

Tipos de trabajos:
Crecimiento

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La energa Trabajo
de Se transforma en Calor
nutrientes Desorden

Tipos de trabajos:
Espermatozoides
Crecimiento

Reproduccin
Produccin: Leche, Lana, Carne, Huevos

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La energa Trabajo
de Se transforma en Calor
nutrientes Desorden

Tipos de trabajos:
Espermatozoides
Crecimiento
Movimiento
Reproduccin
Produccin: Leche, Lana, Carne, Huevos

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ORDEN
La energa Trabajo
de nutrientes Se transforma en Calor
Desorden

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La energa Trabajo
de nutrientes Se transforma en Calor
Desorden

Tres definiciones termodinmicas

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La energa Trabajo
de nutrientes Se transforma en Calor
Desorden

Tres definiciones termodinmicas


1. Energa libre (G),
Energia capaz de realizar trabajo

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La energa Trabajo
de nutrientes Se transforma en Calor
Desorden

Tres definiciones termodinmicas


1. Energa libre (G),
Energia capaz de realizar trabajo
2. Entalpa (H heat)
contenido calrico del sistema

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La energa Trabajo
de nutrientes Se transforma en Calor
Desorden

Tres definiciones termodinmicas


1. Energa libre (G),
Energia capaz de realizar trabajo
2. Entalpa (H heat)
contenido calrico del sistema
3. Entropa (S) ......
expresin cuantitativa del estado de
desorden de un sistema.
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La energa Trabajo
de nutrientes Se transforma en Calor
Desorden

Tres definiciones termodinmicas


1. Energa libre (G),
Energia capaz de realizar trabajo
2. Entalpa (H heat)
contenido calrico del sistema
3. Entropa (S) ......
expresin cuantitativa del estado de
desorden de un sistema.
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Estado inicial y final del sistema:
Variaciones ( )
C6H12O6 + 6 O2 6 CO2 + 6 H2O

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Estado inicial y final del sistema:
Variaciones ( )
C6H12O6 + 6 O2 6 CO2 + 6 H2O

= G

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Estado inicial y final del sistema:
Variaciones ( )
C6H12O6 + 6 O2 6 CO2 + 6 H2O

Energa final (Gf) Energa inicial (Gi) = G

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Estado inicial y final del sistema:
Variaciones ( )
C6H12O6 + 6 O2 6 CO2 + 6 H2O

Energa final (Gf) Energa inicial (Gi) = G

Calor final (Hf) Calor inicial (Hi) = H

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Estado inicial y final del sistema:
Variaciones ( )
C6H12O6 + 6 O2 6 CO2 + 6 H2O

Energa final (Gf) Energa inicial (Gi) = G

Calor final (Hf) Calor inicial (Hi) = H

Entropa final (Sf) Entropa inicial (Si) = S

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Estado inicial y final del sistema:
Variaciones ( )
C6H12O6 + 6 O2 6 CO2 + 6 H2O

Energa final (Gf) Energa inicial (Gi) = G

Calor final (Hf) Calor inicial (Hi) = H

Entropa final (Sf) Entropa inicial (Si) = S

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Entropa (S)
Expresin cuantitativa del desorden de un
sistema.

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Entropa (S)
Expresin cuantitativa del desorden de un
sistema.
A B S = +

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Entropa (S)
Expresin cuantitativa del desorden de un
sistema.
A B S = +

C6H12O6 + 6 O2 6 CO2 + 6 H2O

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Entropa (S)
Expresin cuantitativa del desorden de un
sistema. Proceso espontneo

A B S = +
+ complejos + simples
+ ordenados + desordenados Ganancia de entropa

C6H12O6 + 6 O2 6 CO2 + 6 H2O

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Entropa (S)
Expresin cuantitativa del desorden de un
sistema. Proceso espontneo

A B S = +
+ complejos + simples
+ ordenados + desordenados Ganancia de entropa

C6H12O6 + 6 O2 6 CO2 + 6 H2O


Ms libertad de
movimiento
molecular
7 12 Aumento del No de molculas
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Entropa (S)
Expresin cuantitativa del desorden de un
sistema.
A B S = +
+ complejos + simples
+ ordenados + desordenados Ganancia de entropa

Los organismos vivos son estructuras ordenadas?

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Entropa (S)
Expresin cuantitativa del desorden de un
sistema.
A B S = +
+ complejos + simples
+ ordenados + desordenados Ganancia de entropa

Los organismos vivos son estructuras ordenadas?


Nada en la vida es gratis!

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Entropa (S)
Expresin cuantitativa del desorden de un
sistema.
A B S = +
+ complejos + simples
+ ordenados + desordenados Ganancia de entropa

Los organismos vivos son estructuras ordenadas?


Nada en la vida es gratis!
Conservan su orden interno tomando energa de nutrientes
y devolviendo al entorno una cantidad igual de energa en
forma de calor y entropa!
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Entalpa (H)
Es el contenido calrico del sistema
reaccionante:

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Entalpa (H)
Es el contenido calrico del sistema
reaccionante:
Si libera calor:
Cuando la energa en forma de calor es cedida por el sistema

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Entalpa (H)
Es el contenido calrico del sistema
reaccionante:
Si libera calor: exotrmica (H < 0)
Cuando la energa en forma de calor es cedida por el sistema

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Entalpa (H)
Es el contenido calrico del sistema
reaccionante:
Si libera calor: exotrmica (H < 0)
Cuando la energa en forma de calor es cedida por el sistema

Si adquiere calor:
Es el calor ganado por el sistema

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Entalpa (H)
Es el contenido calrico del sistema
reaccionante:
Si libera calor: exotrmica (H < 0)
Cuando la energa en forma de calor es cedida por el sistema

Si adquiere calor: endotrmica (H > 0)


Es el calor ganado por el sistema

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Entalpa (H)
Es el contenido calrico del sistema
reaccionante:
Si libera calor: exotrmica (H < 0)
Cuando la energa en forma de calor es cedida por el sistema

Si adquiere calor: endotrmica (H > 0)


Es el calor ganado por el sistema

C6H12O6 (s) + 6 O2 (g) 6 CO2 (g) + 6 H2O (l)


H= - 673 Kcal.

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Energa libre de Gibbs (G)
Cantidad de energa capaz de realizar trabajo
durante una reaccin a presin y temperatura
cte.

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Energa libre de Gibbs (G)
Cantidad de energa capaz de realizar trabajo
durante una reaccin a presin y temperatura
cte.
Es la energa que usan las clulas

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Energa libre de Gibbs (G)
Cantidad de energa capaz de realizar trabajo
durante una reaccin a presin y temperatura
cte.
Es la energa que usan las clulas
Predice:
1. La direccin de la reaccin qumica

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Energa libre de Gibbs (G)
Cantidad de energa capaz de realizar trabajo
durante una reaccin a presin y temperatura
cte.
Es la energa que usan las clulas
Predice:
1. La direccin de la reaccin qumica
2. Su posicin exacta de equilibrio

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Energa libre de Gibbs (G)
Cantidad de energa capaz de realizar trabajo
durante una reaccin a presin y temperatura
cte.
Es la energa que usan las clulas
Predice:
1. La direccin de la reaccin qumica
2. Su posicin exacta de equilibrio
3. La cantidad de trabajo desarrollada

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Energa libre de Gibbs (G)
Cantidad de energa capaz de realizar trabajo
durante una reaccin a presin y temperatura
cte.
Es la energa que usan las clulas
Predice:
1. La direccin de la reaccin qumica
2. Su posicin exacta de equilibrio
3. La cantidad de trabajo desarrollada

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Cules son las condiciones bajo las
que se producen en forma espontnea
los procesos vitales?

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Energa libre de Gibbs (G) 1878

Es el indicador de espontaneidad requerido para los


procesos con temperatura y presin constantes.

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Energa libre de Gibbs (G) 1878
A B

G = GB - GA
- = reaccin exergnica (espontnea)
Pueden realizar trabajo

+ = reaccin endergnica

0 = proceso en equilibrio

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Estado inicial y final del sistema:
Variaciones ( )
C6H12O6 + 6 O2 6 CO2 + 6 H2O

Energa final (Gf) Energa inicial (Gi) = G

Calor final (Hf) Calor inicial (Hi) = H

Entropa final (Sf) Entropa inicial (Si) = S

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En sistemas biolgicos (T y P cte.), las variaciones de G, H y S
estn relacionadas por la ecuacin:

G = H - T S

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En sistemas biolgicos (T y P cte.), las variaciones de G, H y S
estn relacionadas por la ecuacin:

G = H - T S

Energa disponible para


Realizar trabajo

Indica:
El gradiente de concentracin mxima que puede generar
La actividad muscular mxima que puede generar
La separacin mxima de carga que puede establecer, etc.

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G = H - T S 1 cal = 4.184 J
kJ/mol kJ/mol K kJ/mol.K

1. G
( - ) reaccin libera energia libre = exergnica
(+) reaccin gana energia libre = endergonica
2. H
( - ) reaccin libera calor = exotrmica
(+) reaccin gana calor = endotrmica
3. S
( + ) reaccin aumenta entropa (P > desordenados S)
( - ) reaccin disminuye entropa

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C6H12O6 + 6 O2 6 CO2 + 6 H2O

G = H - T S
- - +
Reaccin Reaccin Reaccin
exergnica exotrmica aumenta entropa

Reaccin es favorable,
sistema reacciona de forma espontnea

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6 CO2 + 6 H2O C6H12O6 + 6 O2

G = H - T S

+ + -
Reaccin Reaccin Reaccin
endergnica endotrmica disminuye entropa
Reaccin NO es favorable
Reaccin tiende a transcurrir en sentido inverso

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G = H - TS

Signos: - - +

Proceso favorable
2da Ley:
todo proceso que ocurre espontneamente es
capaz de realizar trabajo
G es una medida de la capacidad del sistema para producir
trabajo, sirve para determinar si una reaccin puede o no
ocurrir espontneamente
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La G depende de las condiciones

1) Variacin de Energa Libre en condiciones Estndar y a pH corregido


G

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La G depende de las condiciones

1) Variacin de Energa Libre en condiciones Estndar y a pH corregido


G

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La G depende de las condiciones

1) Variacin de Energa Libre en condiciones Estndar y a pH corregido


G

2) Variacin de Energa Libre Real


G

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G

G = G final - G inicial

Si G es negativa (-) : los productos tienen


menos energa libre que los reactivos y ...

Qu pasara si el G fuera positivo?

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G
G=-RTlnKeq

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G
G = - R T ln Keq
En condiciones estndar:

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G
G = - R T ln Keq
En condiciones estndar:
reactivos y productos 1 M
1 atm
(temperatura absoluta) T = 298 K, en grados K
(25 C)
pH corregido: [H+] 1M pH=0
pH biolgico = 7 [ H+] 10-7 M

R = 8.315 J/mol (constante gases)

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G
G = - R T ln Keq
En condiciones estndar:
reactivos y productos 1 M
1 atm
(temperatura absoluta) T = 298 K, en grados K
(25 C)
pH corregido: [H+] 1M pH=0
pH biolgico = 7 [ H+] 10-7 M

R = 8.315 J/mol (constante gases)

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G
G = - R T ln Keq
En condiciones estndar:
reactivos y productos 1 M
1 atm
(temperatura absoluta) T = 298 K, en grados K
(25 C)
pH corregido: [H+] 1M pH=0
pH biolgico = 7 [ H+] 10-7 M

R = 8.315 J/mol (constante gases)

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G
G = - R T ln Keq
En condiciones estndar:
reactivos y productos 1 M
1 atm
(temperatura absoluta) T = 298 K, en grados K
(25 C)
pH corregido: [H+] 1M pH=0

R = 8.315 J/mol (constante gases)

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G
G = - R T ln Keq
En condiciones estndar:
reactivos y productos 1 M
1 atm
(temperatura absoluta) T = 298 K, en grados K
(25 C)
pH corregido: [H+] 1M pH=0
pH biolgico = 7 [ H+] 10-7 M

R = 8.315 J/mol (constante gases)

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G
G = - R T ln Keq
En condiciones estndar:
reactivos y productos 1 M
1 atm
(temperatura absoluta) T = 298 K, en grados K
(25 C)
pH corregido: [H+] 1M pH=0
pH biolgico = 7 [ H+] 10-7 M

R = 8.315 J/mol (constante gases)

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G = - R T ln Keq
En condiciones estndar:
Los reactivos y productos 1 M
Inicial aA + bB cC + dD

Final

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G = - R T ln Keq
En condiciones estndar:
Los reactivos y productos 1 M
Inicial aA + bB cC + dD

Final

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G = - R T ln Keq
En condiciones estndar:
Los reactivos y productos 1 M
Inicial aA + bB cC + dD

la fuerza propulsora del


G sistema hacia el equilibrio es:
G, es la fuerza motriz.

Final

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G = - R T ln Keq
En condiciones estndar:
Los reactivos y productos 1 M
Inicial aA + bB cC + dD

La relacin de productos y reactivos inicial cambia al final de


G acuerdo a su Keq.

Es una constante de cada reaccin

Final
Keq = [ C ]c [ D ]d
[ A ]a [ B ]b

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G = - R T ln Keq
En condiciones estndar:
Los reactivos y productos 1 M
Inicial Glucosa 1-P Glucosa 6-P
1 1
G
Glucosa 1-P Glucosa 6-P
1 19
Final
Keq = G6P = 19 = 19
G1P 1
G = - (8.315 J/mol.K) (298 K) (ln 19)
G = - 7300 J/mol o -7.3 kJ/mol
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G = - R T ln Keq
En condiciones estndar:
Los reactivos y productos 1 M
Inicial Glucosa 1-P Glucosa 6-P
1 1
G
Glucosa 1-P Glucosa 6-P
1 19
Final G = - (8.315 J/mol.K) (298 K) (ln 19)
G = - 7300 J/mol o -7.3 kJ/mol

Como es esta reaccin? Es favorable?


Que valor de G tendra la inversa?
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G est directamente relacionada con la Keq

G = - RT ln Keq

aA + bB cC + dD

Keq = [ C ]c [ D ]d
[ A ]a [ B ]b

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a, b, c y d son el nmero de molculas de A, B, C y D que participan.
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G est directamente relacionada con la Keq

forma alternativa de
G = - RT ln Keq
expresar la Keq.
aA + bB cC + dD

Keq = [ C ]c [ D ]d
[ A ]a [ B ]b

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G est directamente relacionada con la Keq

forma alternativa de
G = - RT ln Keq
expresar la Keq.

Keq = [ C ]c [ D ]d
[ A ]a [ B ]b

Keq G Reaccin
K<1 Positiva (+) se favorece la formacin de reactivos.
K>1 Negativa (-) se favorece la formacin de productos
K=1 Cero se encuentra en equilibrio

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G est directamente relacionada con la Keq

forma alternativa de
G = - RT ln Keq
expresar la Keq.

Keq = [ C ]c [ D ]d
[ A ]a [ B ]b

Keq G Reaccin
K<1 Positiva (+) se favorece la formacin de reactivos.
K>1 Negativa (-) se favorece la formacin de productos
K=1 Cero se encuentra en equilibrio

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G est directamente relacionada con la Keq

forma alternativa de
G = - RT ln Keq
expresar la Keq.

Keq = [ C ]c [ D ]d
[ A ]a [ B ]b

Keq G Reaccin
K<1 Positiva (+) se favorece la formacin de reactivos.
K>1 Negativa (-) se favorece la formacin de productos
K=1 Cero se encuentra en equilibrio

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G
G = G final - G inicial

La Variacin de Energa Libre en condiciones estndar nos


dice en qu direccin y hasta que punto debe transcurrir
determinada reaccin para alcanzar el equilibrio cuando la
concentracin inicial de cada componente es 1 M, a pH 7,0
y a 298 K, y a presin 101.3 kPa (1atm).

Nos dice la energa disponible en condiciones estndares;


pero no en las condiciones reales en las clulas

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G
VARIACION DE ENERGIA LIBRE REAL

La energa liberada en las condiciones que


existen en las clulas.
De que depende la Variacin de energa
libre real?

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VARIACION DE ENERGIA LIBRE REAL, G
G = G + RT ln [C][D]
[A][B]

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VARIACION DE ENERGIA LIBRE REAL, G
G = G + RT ln [C][D]
[A][B]
Temperatura (K) en la cual
se desarrolla la reaccin

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VARIACION DE ENERGIA LIBRE REAL, G
G = G + RT ln [C][D] Q
[A][B]
Temperatura (K) en la cual Concentraciones Iniciales de Reacitvos
se desarrolla la reaccin y Productos en condiciones reales!

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VARIACION DE ENERGIA LIBRE REAL, G
G = G + RT ln [C][D] Q
[A][B]
Temperatura (K) en la cual Concentraciones Iniciales de Reacitvos
se desarrolla la reaccin y Productos en condiciones reales!

R = 8.315 J/mol.K R = 1,987 cal/mol.K

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VARIACION DE ENERGIA LIBRE REAL, G
G = G + RT ln [C][D] Q
[A][B]
Temperatura (K) en la cual Concentraciones Iniciales de Reacitvos
se desarrolla la reaccin y Productos en condiciones reales!

R = 8.315 J/mol.K R = 1,987 cal/mol.K

Espontaneidad de las reacciones en condiciones reales


El criterio para la espontaneidad es?
G
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G = G + RT ln [C][D] Q
[A][B]
G = - RT ln Keq

Condiciones estndar Lo que se da realmente en el


Sistema de observacin
Trmino constante
Trmino variable

Temperatura
Depende:
Q
ESPONTANEIDAD DE UNA REACCIN = G
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Estado inicial

G = G + RT ln [C][D] Q
[A][B]
G = - RT ln Keq

Condiciones estndar Lo que se da realmente en el


Sistema de observacin
Trmino constante
Trmino variable

G = 0 G = - RT ln Q

Keq

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Estado inicial

G = G + RT ln [C][D] Q
[A][B]
G = - RT ln Keq

Condiciones estndar Lo que se da realmente en el


Sistema de observacin
Trmino constante
Trmino variable

G = 0 G = - RT ln Q

-G/RT
Keq= [C][D] = e Keq
[A][B]
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Espontaneidad de las reacciones
G = G + RT ln [C][D]
[A][B]
+
Puede una reaccin ocurrir espontneamente siendo su G +?

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Espontaneidad de las reacciones
G = G + RT ln [C][D]
[A][B]
+
Valor negativo y > G
-
Espontnea
G depende de:
la concentraciones de reactivos y
productos,
y de la temperatura durante la reaccin.
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G
Cantidad de energa capaz de realizar
trabajo

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G
Cantidad de energa capaz de realizar
trabajo

Toda G es aprovechada para realizar


trabajo?

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G
Cantidad de energa capaz de realizar
trabajo

Toda G es aprovechada para realizar


trabajo?
NO. No existe ningn sistema capaz de
aprovechar 100% esa energa.

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G
Cantidad de energa capaz de realizar
trabajo

Toda G es aprovechada para realizar


trabajo?
NO. No existe ningn sistema capaz de
aprovechar 100% esa energa.
Qu pasa entonces con el resto de
energa que no es aprovechada?
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G
Cantidad de energa capaz de realizar trabajo

Toda G es aprovechada para realizar


trabajo?
NO. No existe ningn sistema capaz de
aprovechar 100% esa energa.
Qu pasa entonces con el resto de energa
que no es aprovechada?
Se pierde en forma de Calor (ejemplo).

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Una reaccin termodinmicamente desfavorable
(endergnica) cmo puede ser impulsada en la
direccin directa?

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Una reaccin termodinmicamente desfavorable
(endergnica) cmo puede ser impulsada en la
direccin directa?
S, gracias al acoplamiento de reacciones
secuenciales a travs de un intermediario comn.

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Una reaccin termodinmicamente desfavorable
(endergnica) cmo puede ser impulsada en la
direccin directa?
S, gracias al acoplamiento de reacciones
secuenciales a travs de un intermediario comn.

1) A B G1
2) B C G2

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Una reaccin termodinmicamente desfavorable
(endergnica) cmo puede ser impulsada en la
direccin directa?
S, gracias al acoplamiento de reacciones
secuenciales a travs de un intermediario comn.

1) A B G1
Se suman

2) B C G2

A C G1 + G2

Gtotal
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Una reaccin termodinmicamente desfavorable
(endergnica) cmo puede ser impulsada en la
direccin directa?
S, gracias al acoplamiento de reacciones
secuenciales a travs de un intermediario comn.

1) A B G1
Se suman

2) B C G2

A C G1 + G2

Gtotal
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Glucosa+ Pi Glucosa 6-P + H2O G= 13.8 kJ/mol

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Glucosa+ Pi Glucosa 6-P + H2O G= 13.8 kJ/mol

ATP + H2O ADP + Pi G= - 30.5 kJ/mol

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Glucosa+ Pi Glucosa 6-P + H2O G= 13.8 kJ/mol

ATP + H2O ADP + Pi G= - 30.5 kJ/mol

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Las G son aditivas
Glucosa+ Pi Glucosa 6-P + H2O G= 13.8 kJ/mol

ATP + H2O ADP + Pi G= - 30.5 kJ/mol

Glucosa + ATP Glucosa 6-P + ADP G= - 16.7 kJ/mol

La reaccin global es exergnica

La adicin de cambios de energa libre permite que una


reaccin endergnica se dirija por una reaccin
exergnica bajo condiciones apropiadas.
Las dos reacciones estn acopladas por medio de su
intermedio comn.

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Cual de las siguientes reacciones
es la ms rpida?
Reaccin G (Kj/mol)
1 - 13.4
2 -20.0
3 3.7
4 5.2

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Cual de las siguientes reacciones
es la ms rpida?
Reaccin G (Kj/mol)
1 - 13.4
2 -20.0
3 3.7
4 5.2

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Cual de las siguientes reacciones
es la ms rpida?
Reaccin
G (Kj/mol)
1 tema de la-cintica
La velocidad es un 13.4 qumica,
NO de la Termodinmica -20.0
2
3 3.7
4 5.2

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Reactivo Producto
Energa inicial (Gi) Energa final (Gf) G
G = Energa de activacin
Energa libre, G

Reactivo
Gi
Producto
Gf

Coordenada de la reaccin

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Reactivo Producto
Energa inicial (Gi) Energa final (Gf) G
Estado de transicin G = Energa de activacin
Energa libre, G

Reactivo
Gi
Producto
Gf

Coordenada de la reaccin

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Reactivo Producto
Energa inicial (Gi) Energa final (Gf) G
Estado de transicin G = Energa de activacin
Energa libre, G
GSP

Reactivo
Gi
Producto
Gf

Coordenada de la reaccin

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Reactivo Producto
Energa inicial (Gi) Energa final (Gf) G
Estado de transicin G = Energa de activacin
Energa libre, G
GSP

Reactivo
Gi
Producto
Gf

Coordenada de la reaccin

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Reactivo Producto
Energa inicial (Gi) Energa final (Gf) G
Estado de transicin G = Energa de activacin
Energa libre, G
GSP GPS

Reactivo
Gi
Producto
Gf

Coordenada de la reaccin

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Reactivo Producto
Energa inicial (Gi) Energa final (Gf) G
Estado de transicin G = Energa de activacin
Energa libre, G
GSP GPS

Reactivo
Gi G
Producto
Gf

Coordenada de la reaccin

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Reactivo Producto
Energa inicial (Gi) Energa final (Gf) G
Estado de transicin G = Energa de activacin
Energa libre, G
GSP GPS

Inicial
Reactivo
G Gi G
Final Producto
Gf

Coordenada de la reaccin
la fuerza propulsora del
sistema hacia el equilibrio es:
G, es la fuerza motriz.
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Ej: combustin lea muy favorable termodinamicamente,
pero es estable ENERGIA DE ACTIVACION (G) es
superior a la disponible a temperatura ambiente.

Y en la CELULA?
COMO VENCEMOS ESTA G ???

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Ejercicios

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1) Cual es el G de hidrlisis del ATP?
ATP + H2O ADP + Pi

Glucosa 6-P + H2O Glucosa + Pi Keq= 270 G ?

glucosa + ATP glucosa 6-P + ADP Keq= 890 G ?

ATP + H2O ADP + Pi G ?

G = - RT ln Keq

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1) Cual es el G de hidrlisis del ATP?
ATP + H2O ADP + Pi

Glucosa 6-P + H2O Glucosa + Pi Keq= 270 G ?

glucosa + ATP glucosa 6-P + ADP Keq= 890 G ?

ATP + H2O ADP + Pi G ?

G = - RT ln Keq

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1) Cual es el G de hidrlisis del ATP?
G = - RT ln Keq
Glucosa 6-P + H2O Glucosa + Pi Keq= 270
G = - 8.135 x 10-3 kJ X 298 K X ln 270 = - 13.57 kJ/mol
mol.K

glucosa + ATP glucosa 6-P + ADP Keq= 890

G = - 8.135 x 10-3 kJ X 298 K X ln 890 = - 16.46 kJ/mol


mol.K

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1) Cual es el G de hidrlisis del ATP?
ATP + H2O ADP + Pi

Glucosa 6-P + H2O Glucosa + Pi G = - 13.57 kJ/mol

glucosa + ATP glucosa 6-P + ADP G = - 16.46 kJ/mol

ATP + H2O ADP + Pi G = - 30 kJ/mol

Como es esta reaccin? Es favorable?


Que valor de G tendra la inversa?

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2) G de hidrlisis del ATP en glbulos rojos

ATP + H20 ADP + Pi


[ mM] 2.25 0.25 + 1.65

G = G + RT ln [ADP][Pi]
[ATP]
G = - 30.500 J/mol+ (8.315 J/mol.K)(298 K)ln 1.83 X10-4

G = - 51.800 J/mol

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Resumen 1
Los organismos vivos crean y mantienen sus estructuras
complejas y ordenadas a expensas de la energa que
extraen de los combustibles.
En cualquier proceso fsico o qumico la cantidad de
energa total del universo permanece constante, pero
puede transformarse.
Las clulas son mquinas qumicas que funcionan a
temperatura y presin constantes, e intercambian energa
y materia con el entorno (nunca estan en equilibrio).
En todos los procesos la entropa del universo aumenta, el
orden de los seres vivos se obtiene a expensas del
desorden del entorno.

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Resumen 2

G es la variacin de energa cuando el sistema se mueve


desde su estado inicial al de equilibrio.

La magnitud de la G depende de la reaccin qumica


especfica y de lo lejos del equilibrio que est el sistema
inicialmente.

G nos informa respecto si la reaccin ( en condiciones


estandar) es favorable o no.

G: depende de concentraciones de reactivos y productos,


y de la temperatura en la que se de la reaccin

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Muchas gracias!!!

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No confundir
Equilibrios de reaccin asociados
a G (energa libre)

Velocidades de reaccin asociados


a G (Energa de activacin)

Un valor grande negativo de G refleja un equilibrio de


reaccin FAVORABLE
Pero NO significa que la reaccin transcurra a una
velocidad alta

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Las Keq son multiplicativas
Glucosa+ Pi Glucosa 6-P + H2O Keq1= 3.9 x 10-3 M-1

ATP + H2O ADP + Pi Keq2= 2.5 x 105 M

Glucosa + ATP Glucosa 6-P + ADP Keq3 =Keq1 x Keq2

8.315 x 10-3 Kj/Mol.K 298 Keq3 = 7.8 x 102

G = - R T ln Keq

G = - 16.5 Kj/mol

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Clasificacin de los organismos vivos segn
la forma de obtener carbono
CO2
Comp. inorgnicos

H2O

O2
Ej. Glucosa

Comp. orgnicos
Auttrofos Hetetrofos
Autoalimentados Alimentados a partir de otros

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Reactivo Producto
Energa inicial (Gi) Energa final (Gf) G
G = Energa de activacin
Energa libre, G

Reactivo
Gi
Producto
Gf

Coordenada de la reaccin

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