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TRAPP: CHAP04 2006/3/8 17:05 PAGE 81 #1

4
Physical transformations
of pure substances
Answers to discussion questions
D4.1 Consider two phases of a system, labeled and . The phase with the lower chemical potential under
the given set of conditions is the more stable phase. First consider the variation of with temperature
at a xed pressure. We have
_

T
_
p
= S

and
_

T
_
p
= S

.
Therefore, if S

is larger in magnitude than S

, the phase will be favored over the phase as temperature


increases because its chemical potential decreases more rapidly with temperature than for the phase.
We also have
_

P
_
T
= V
m,
and
_

P
_
T
= V
m,
.
Therefore, if V
m,
is larger than V
m,
the phase will be favored over the phase as pressure increases
because the chemical potential of the phase will not increase as rapidly with pressure as that of the
phase. See Example 4.1.
D4.3 Refer to Fig. 4.1 above and Fig. 4.5 in the text. Starting at point A and continuing clockwise on path
p(T) toward point B, we see a gaseous phase only within the container with water at pressures and
temperatures p(T). Upon reaching point B on the vapor pressure curve, liquid appears on the bottom of
the container and a phase boundary or meniscus is evident between the liquid and less dense gas above
it. The liquid and gaseous phases are at equilibrium at this point. Proceeding clockwise away from the
vapor pressure curve the meniscus disappears and the system becomes wholly liquid. Continuing along
p(T) to point C at the critical temperature no abrupt changes are observed in the isotropic uid. Before
point C is reached, it is possible to return to the vapor pressure curve and a liquidgas equilibrium by
reducing the pressure isothermally. Continuing clockwise from point C along path p(T) back to point A,
no phase boundary is observed even though we now consider the water to have returned to the gaseous
state. Additionally, if the pressure is isothermally reduced at any point after point C, it is impossible to
return to a liquidgas equilibrium.
When the path p(T) is chosen to be very close to the critical point, the water appears opaque. At near
critical conditions, densities and refractive indices of both the liquid and gas phases are nearly identical.
Furthermore, molecular uctuations cause spatial variations of densities and refractive indices on a scale
large enough to strongly scatter visible light. This is called critical opalescence.
TRAPP: CHAP04 2006/3/8 17:05 PAGE 82 #2
82 SOLUTIONS MANUAL
A
B
C
Critical point
Exploration
Path p(T)
Vapor pressure curve of water
221.2 bar
647.4 K
p
T
Figure 4.1 Vapor pressure curve of water
D4.5 The supercritical uid extractor consists of a pump to pressurize the solvent (e.g. CO
2
), an oven with
extractionvessel, anda trappingvessel. Extractions are performeddynamicallyor statically. Supercritical
uid ows continuously through the sample within the extraction vessel when operating in dynamic
mode. Analytes extracted into the uid are released through a pressure-maintaining restrictor into a
trapping vessel. In static mode the supercritical uid circulates repetitively through the extraction vessel
until being released into the trapping vessel after a period of time. Supercritical carbon dioxide volatilizes
when decompression occurs upon release into the trapping vessel.
Advantages Disadvantages Current uses
Dissolving power of SCF can
be adjusted with selection of T
and p
Elevated pressures are required
and the necessary apparatus
expensive
Extraction of caffeine, fatty
acids, spices, aromas, avors,
and biological materials from
natural sources
Select SCFs are inexpensive
and non-toxic. They reduce
pollution
Cost may prohibit large scale
applications
Extraction of toxic salts (with
a suitable chelation agent) and
organics from contaminated
water
Thermally unstable analytes
may be extracted at low
temperature
Modiers like methanol (110%)
may be required to increase
solvent polarity
Extraction of herbicides from
soil
The volatility of scCO
2
makes
it easy to isolate analyte
scCO
2
is toxic to whole cells in
biological applications (CO
2
is not
toxic to the environment)
scH
2
O oxidation of toxic,
intractable organic waste
during water treatment
SCFs have high diffusion rates,
low viscosity, and low surface
tension
Synthetic chemistry, polymer
synthesis and crystallization,
textile processing
O
2
and H
2
are completely
miscible with scCO
2
. This
reduces multi-phase reaction
problems
Heterogeneous catalysis for
green chemistry processes
TRAPP: CHAP04 2006/3/8 17:05 PAGE 83 #3
PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES 83
D4.7 First-order phase transitions showdiscontinuities in the rst derivative of the Gibbs energy with respect to
temperature. They are recognized by nite discontinuities in plots of H, U, S, and V against temperature
and by an innite discontinuity in C
p
. Second-order phase transitions show discontinuities in the second
derivatives of the Gibbs energy with respect to temperature, but the rst derivatives are continuous. The
second-order transitions are recognized by kinks in plots of H, U, S, and V against temperature, but most
easily by a nite discontinuity in a plot of C
p
against temperature. A -transition shows characteristics
of both rst- and second-order transitions and, hence, is difcult to classify by the Ehrenfest scheme. It
resembles a rst-order transition in a plot of C
p
against T, but appears to be a higher-order transition
with respect to other properties.
At the molecular level rst-order transitions are associated with discontinuous changes in the interaction
energies between the atoms or molecules constituting the systemand in the volume they occupy. One kind
of second-order transition may involve only a continuous change in the arrangement of the atoms from
one crystal structure (symmetry) to another while preserving their orderly arrangement. In one kind of
8-transition, called an orderdisorder transition, randomness is introduced into the atomic arrangement.
See Figs. 4.18 and 4.19 of the text.
Solutions to exercises
E4.1(a) On the assumption that the vapor is a perfect gas and that
vap
H is independent of temperature, we
may write
p = p

, =
_

vap
H
R
_

_
1
T

1
T

_
[4.12], ln
p

p
= .
1
T
=
1
T

+
R

vap
H
ln
p

p
=
1
297.25 K
+
_
8.314 J K
1
mol
1
28.7 10
3
J mol
1
_
ln
53.3 kPa
70.0 kPa
= 3.285 10
3
K
1
.
Hence, T = 304 K = 31

C .
E4.2(a)
dp
dT
=

trs
S

trs
V
[4.6].

fus
S =
fus
V
_
dp
dT
_

fus
V
p
T
[
fus
S and
fus
V assumed independent of temperature].

fus
S = [(163.3 161.0) 10
6
m
3
mol
1
]
_
(100 1) (1.013 10
5
Pa)
(351.26 350.75) K
_
= +45.23 J K
1
mol
1
.

fus
H = T
f
S = (350.75 K) (45.23 J K
1
mol
1
) = +16 kJ mol
1
.
TRAPP: CHAP04 2006/3/8 17:05 PAGE 84 #4
84 SOLUTIONS MANUAL
E4.3(a) The expression for ln p is the indenite integral of eqn 4.11,
_
d ln p =
_

vap
H
RT
2
dT; ln p = constant

vap
H
RT
.
Therefore,
vap
H = (2501.8 K) R = (2501.8 K) (8.314 J K
1
mol
1
) = +20.80 kJ mol
1
.
E4.4(a) (a) The indenitely integrated form of eqn 4.11 is used as in Exercise 4.3(a).
ln p = constant

vap
H
RT
, or log p = constant

vap
H
2.303RT
.
Therefore,

vap
H = (2.303) (1780 K) R = (2.303) (1780 K) (8.314 J K
1
mol
1
)
= +34.08 kJ mol
1
.
(b) The boiling point corresponds to p = 1.000 atm = 760 Torr.
log 760 = 7.960
1780 K
T
b
, T
b
= 350.5 K .
E4.5(a)
T

fus
V

fus
S
p [4.6, and Exercise 4.2(a)]

T
f

fus
V

fus
H
p =
T
f
pM

fus
H
=
_
1

_
[V
m
= M/]

_
(278.6 K) (999) (1.013 10
5
Pa) (78.12 10
3
kg mol
1
)
10.59 10
3
J mol
1
_

_
1
879 kg m
3

1
891 kg m
3
_
3.18 K.
Therefore, at 1000 atm, T
f
(278.6 +3.18) K = 281.8 K [8.7

C].
E4.6(a) The rate of loss of mass of water may be expressed as
dm
dt
=
dn
dt
M
H
2
O
; n =
q

vap
H
.
dn
dt
=
(dq/dt)

vap
H
=
(1.2 10
3
Wm
2
) (50 m
2
)
44.0 10
3
J mol
1
= 1.4 mols
1
.
dm
dt
= (1.4 mols
1
) (18.02 g mol
1
) = 25 g s
1
.
E4.7(a) Assume perfect gas behavior.
n =
pV
RT
, n =
m
M
, V = 75 m
3
.
m =
pVM
RT
.
TRAPP: CHAP04 2006/3/8 17:05 PAGE 85 #5
PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES 85
(a) m =
(3.2 kPa) (75 m
3
) (18.02 10
3
kg mol
1
)
(8.314 10
3
kPa K
1
mol
1
) (298.15 K)
= 1.7 kg .
(b) m =
(13.1 kPa) (75 m
3
) (78.11 10
3
kg mol
1
)
(8.314 10
3
kPa K
1
mol
1
) (298.15 K)
= 31 kg .
(c) m =
(0.23 Pa) (75 m
3
) (200.59 g mol
1
)
(8.314 Pa m
3
K
1
mol
1
) (298.15 K)
= 1.4 g .
Question. Assuming all the mercury vapor breathed remains in the body, how long would it take to
accumulate 1.4 g? Make reasonable assumptions about the volume and frequency of a breath.
E4.8(a) The ClausiusClapeyron equation [4.11] integrates to the form [4.12] which may be rewritten as
ln
_
p
2
p
1
_
=

vap
H
R

_
1
T
1

1
T
2
_
.
(a)
ln
_
40 kPa
10 kPa
_
=
_

vap
H
8.314 J K
1
mol
1
_

_
1
359.0 K

1
392.5 K
_
,
1.405 =
vap
H (2.86 10
5
J
1
mol),

vap
H = 49.1 kJ mol
1
.
(b) The normal boiling point corresponds to a vapor pressure of 760 Torr. Using the data at 119.3

C
ln
_
101.3 kPa
5.3 kPa
_
=
_
49.1 10
3
J mol
1
8.314 J K
1
mol
1
_

_
1
392.5 K

1
T
b
_
,
2.950 = 15.04
5905 K
T
b
; T
b
= 488 K = 215

C .
[The accepted value is 218

C.]
(c)

vap
S(T
b
) =

vap
H(T
b
)
T
b

49.1 10
3
J mol
1
488 K
= 101 J K
1
mol
1
.
E4.9(a)
T = T
f
(50 bar) T
f
(1 bar)
T
f
pM

fus
H

_
1

_
[Exercise 4.5(a)],

fus
H = 6.01 kJ mol
1
[Table 2.3],
T =
_
(273.15 K) (49 10
5
Pa) (18 10
3
kg mol
1
)
6.01 10
3
J mol
1
_

_
1
1.00 10
3
kg m
3

1
9.2 10
2
kg m
3
_
= 0.35 K.
T
f
(50 bar) = (273.15 K) (0.35 K) = 272.80 K .
TRAPP: CHAP04 2006/3/8 17:05 PAGE 86 #6
86 SOLUTIONS MANUAL
E4.10(a)
vap
H =
vap
U +
vap
(pV) = 40.656 kJ mol
1
[Table 2.3]

vap
(pV) = p
vap
V = p(V
gas
V
liq
) pV
gas
= RT [per mole, perfect gas]
= (8.314 J K
1
mol
1
) (373.2 K) = 3.102 10
3
kJ mol
1
Fraction =

vap
(pV)

vap
H
=
3.102 10
3
kJ mol
1
40.656 kJ mol
1
= 0.07630 7.6 per cent
Solutions to problems
Solutions to numerical problems
P4.1 At the triple point, T
3
, the vapor pressures of liquid and solid are equal; hence
10.5916
1871.2 K
T
3
= 8.3186
1425.7 K
T
3
; T
3
= 196.0 K .
log(p
3
/Torr) =
1871.2 K
196.0 K
+10.5916 = 1.0447; p
3
= 11.1 Torr .
P4.3 (a)
dp
dT
=

vap
S

vap
V
=

vap
H
T
b

vap
V
[4.6, Clapeyron equation]
=
14.4 10
3
J mol
1
(180 K)
_
14.5 10
3
1.15 10
4
_
m
3
mol
1
= +5.56 kPa K
1
.
(b)
dp
dT
=

vap
H
RT
2
p
_
4.11, with d ln p =
dp
p
_
=
_
14.4 10
3
J mol
1
_

_
1.013 10
5
Pa
_
_
8.314 J K
1
mol
1
_
(180 K)
2
= +5.42 kPa K
1
.
The percentage error is 2.5 per cent .
P4.5 (a)
_
(1)
p
_
T

_
(s)
p
_
T
= V
m
(l) V
m
(s)[4.13] = M
_
1

_
=
_
18.02 g mol
1
_

_
1
1.000 g cm
3

1
0.917 g cm
3
_
= 1.63 cm
3
mol
1
.
(b)
_
(g)
p
_
T

_
(l)
p
_
T
= V
m
(g) V
m
(l)
=
_
18.02 g mol
1
_

_
1
0.598 g dm
3

1
0.958 10
3
g dm
3
_
= +3.01 dm
3
mol
1
.
TRAPP: CHAP04 2006/3/8 17:05 PAGE 87 #7
PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES 87
At 1.0 atm and 100

C, (l) = (g); therefore, at 1.2 atm and 100

C, (g) (1) V
vap
p =
(as in Problem 4.4)
(30.1 10
3
m
3
mol
1
) (0.2) (1.013 10
5
Pa) + 0.6 kJ mol
1
.
Since (g) > (l), the gas tends to condense into a liquid.
P4.7 The amount (moles) of water evaporated is n
g
=
p
H
2
O
V
RT
.
The heat leaving the water is q = n
vap
H.
The temperature change of the water is T =
q
nC
p,m
, n =amount of liquid water.
Therefore, T =
p
H
o
2
V
vap
H
RTnC
p,m
=
(3.17 kPa)
_
50.0 dm
3
_

_
44.0 10
3
J mol
1
_
_
8.314 kPa dm
3
K
1
mol
1
_
(298.15 K)
_
75.5 J K
1
mol
1
_
(250 g/18.02 g mol
1
)
= 2.7K.
The nal temperature will be about 22

C .
P4.9 (a) Follow the procedure in Problem 4.8, but note that T
b
= 227.5

C is obvious from the data.


(b) Draw up the following table. The points are plotted in Fig. 4.2. The slope is
/

C 57.4 100.4 133.0 157.3 203.5 227.5


T/K 330.6 373.6 406.2 430.5 476.7 500.7
1000 K/T 3.02 2.68 2.46 2.32 2.10 2.00
ln p/Torr 0.00 2.30 3.69 4.61 5.99 6.63
6.4 10
3
K, so

vap
H
R
= 6.4 10
3
K,
implying that
vap
H = +53 kJ mol
1
.
P4.11 (a) The phase diagram is shown in Fig. 4.3.
(b) The standard melting point is the temperature at which solid and liquid are in equilibrium at 1 bar.
That temperature can be found by solving the equation of the solidliquid coexistence curve for the
temperature
1 = p
3
/bar +1000(5.60 +11.727x)x.
So 11727x
2
+5600x +
_
4.362 10
7
1
_
= 0.
TRAPP: CHAP04 2006/3/8 17:05 PAGE 88 #8
88 SOLUTIONS MANUAL
Figure 4.2
Figure 4.3
The quadratic formula yields
x =
5600
_
(5600)
2
4 (11 727) (1)
_
1/2
2 (11 727)
=
1
_
1 +(4(11 727))/5600
2
_
1/2
2 ((11 727)/5600)
.
The square root is rewritten to make it clear that the square root is of the form {1 +a}
1/2
, with
a 1; thus the numerator is approximately 1 +
_
1 +
1
2
a
_
=
1
2
a, and the whole expression
reduces to
x 1/5600 = 1.79 10
4
.
Thus, the melting point is
T = (1 +x) T
3
= (1.000179) (178.15 K) = 178.18 K .
(c) The standard boiling point is the temperature at which the liquid and vapor are in equilibrium at
1 bar. That temperature can be found by solving the equation of the liquidvapor coexistence curve
for the temperature. This equation is too complicated to solve analytically, but not difcult to solve
numerically with a spreadsheet. The calculated answer is T = 383.6 K .
TRAPP: CHAP04 2006/3/8 17:05 PAGE 89 #9
PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES 89
(d) The slope of the liquidvapor coexistence curve is given by
dp
dT
=

vap
H

T
vap
V

so
vap
H

= T
vap
V

dp
dT
.
The slope can be obtained by differentiating the equation for the coexistence curve.
dp
dT
= p
dlnp
dT
= p
dlnp
dy
dy
dT
,
dp
dT
=
_
10.413
y
2
15.996 +2(14.015)y 3(5.0120)y
2
(1.70) (4.7224) (1 y)
0.70
_

_
p
T
c
_
.
At the boiling point, y = 0.6458, so
dp
dT
= 2.851 10
2
bar K
1
= 2.851 kPa K
1
and
vap
H

= (383.6 K)
_
(30.3 0.12) dm
3
mol
1
1000 dm
3
m
3
_

_
2.851 kPa K
1
_
= 33.0 kJ mol
1
.
Solutions to theoretical problems
P4.13
_
G
p
_
T
=
_
G

p
_
T

_
G

p
_
T
= V

.
Therefore, if V

= V

, G is independent of pressure. In general, V

= V

, so that G is nonzero,
though small, since V

is small.
P4.15 Amount of gas bubbled through liquid =
pV
RT
(p = initial pressure of gas and emerging gaseous mixture).
Amount of vapor carried away =
m
M
.
Mole fraction of vapor in gaseous mixture =
m/M
(m/M) +(pV/RT)
.
Partial pressure of vapor = p =
m/M
(m/M) +(pV/RT)
p =
p (mRT/PVM)
(mRT/PVM) +1
=
mPA
mA +1
, A =
RT
PVM
.
For geraniol, M = 154.2 g mol
1
, T = 383 K, V = 5.00 dm
3
, p = 1.00 atm, and m = 0.32 g, so
A =
_
8.206 10
2
dm
3
atm K
1
mol
1
_
(383 K)
(1.00 atm)
_
5.00 dm
3
_

_
154.2 10
3
kg mol
1
_ = 40.76 kg
1
.
TRAPP: CHAP04 2006/3/8 17:05 PAGE 90 #10
90 SOLUTIONS MANUAL
Therefore
p =
_
0.32 10
3
kg
_
(760 Torr)
_
40.76 kg
1
_
_
0.32 10
3
kg
_

_
40.76 kg
1
_
+1
= 9.8 Torr .
P4.17 In each phase the slopes are given by
_

T
_
p
= S
m
[4.1].
The curvatures of the graphs of
.
against T are given by
_

T
2
_
p
=
_
S
m
T
_
p
=
1
T
C
p,m
[Problem 3.26].
Since C
p,m
is necessarily positive, the curvatures in all states of matter are necessarily negative. C
p,m
is often largest for the liquid state, though not always, but it is the ratio C
p,m
/T that determines the
magnitude of the curvature, so no precise answer can be given for the state with the greatest curvature.
It depends upon the substance.
P4.19 S
m
= S
m
(T, p).
dS
m
=
_
S
m
T
_
p
dT +
_
S
m
p
_
T
dp.
_
S
m
T
_
p
=
C
p,m
T
[Problem 3.26] ,
_
S
m
p
_
T
=
_
V
m
T
_
p
[Maxwell relation] .
dq
rev
= T dS
m
= C
p,m
dT T
_
V
m
T
_
p
dp.
C
S
=
_
q
T
_
s
= C
p,m
TV
m

_
p
T
_
s
= C
p,m
V
m

H
m
V
m
[4.7] .
Solutions to applications
P4.21 (a) The Dieterici equation of state is purported to have good accuracy near the critical point. It does fail
badly at high densities where V
m
begins to approach the value of the Dieterici coefcient b. We will
use it to derive a practical equation for the computations.
p
r
=
e
2
T
r
e
2/T
r
V
r
2V
r
1
[Table 1.7].
Substitution of the Dieterici equation of state derivative (p
r
/T
r
)
V
r
= (2 +T
r
V
r
)p
r
/T
2
r
V
r
into the
reduced form of eqn 3.48 gives
_
U
r
V
r
_
T
r
= T
r
_
p
r
T
r
_
V
r
p
r
=
2p
r
T
r
V
r
(U
r
= U/p
c
V
c
).
TRAPP: CHAP04 2006/3/8 17:05 PAGE 91 #11
PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES 91
Integration along the isotherm T
r
from an innite volume to V
r
yields the practical computational
equation.
U
r
(T
r
, V
r
) =
_

T
r
constant
2p
r
(T
r
, V
r
)
T
r
V
r
dV
r
.
The integration is performed with mathematical software.
(c) (T
r
, V
r
) =

p
c
U
r
/V
r
where p
c
= 72.9 atm.
Carbon dioxide should have solvent properties similar to liquid carbon tetrachloride (8 9)
when the reduced pressure is in the approximate range
0.85 to 0.90 when T
r
= 1
2 (a)
(b)
3
4
5
6
7
0.5 1 1.5 2 2.5 3 3.5 4
T
r
=1.5
T
r
=1.2
p
r
U
r
T
r
=1
4.5
T
r
=1.5
p
r

T
r
=1
0.95 0.9 1 0.85 0.8 0.75
5
10
15
atm

20
Solubility parameter of carbon dioxide
Figure 4.4
TRAPP: CHAP04 2006/3/8 17:05 PAGE 92 #12
92 SOLUTIONS MANUAL
P4.23 C(graphite) C(diamond) ,
r
G

= 2.8678 kJ mol
1
at Tc . Tc = 25

C.
We want the pressure at which
r
G = 0; above that pressure the reaction will be spontaneous. Equation
3.50 determines the rate of change of
r
G with p at constant T.
(1)
_

r
G
p
_
T
=
r
V = (V
D
V
G
)M
where M is the molar mass of carbon; V
D
and V
G
are the specic volumes of diamond and graphite,
respectively.

r
G( Tc , p) may be expanded in a Taylor series around the pressure p

= 100 kPa at Tc .
(2)

r
G( Tc , p) =
r
G

_
Tc , p

_
+
_

r
G
_
Tc , p

_
p
_
T
_
p p

_
+
1
2
_

r
G

(T, p

)
p
2
_
T
_
p p

_
2
+
_
p p

_
3
.
We will neglect the third- and higher-order terms; the derivative of the rst-order term can be
calculated with eqn 1. An expression for the derivative of the second-order term can be derived with
eqn 1.
(3)
_

r
G
p
2
_
T
=
__
V
D
p
_
T

_
V
G
p
_
T
_
M = {V
G

T
(G) V
D

T
(D)} M [2.52 with 2.22].
Calculating the derivatives of eqns 1 and 2 at Tc and p

,
(4)
_

r
G
_
Tc , p

_
p
_
T
= (0.284 0.444)
_
cm
3
g
_

_
12.01 g
mol
_
= 1.92 cm
3
mol
1
,
(5)
_

r
G
_
Tc , p

_
p
2
_
T
= {0.444(3.04 10
8
) 0.284(0.187 10
8
)}

_
cm
3
kPa
1
g
_

_
12.01 g
mol
_
= 1.56 10
7
cm
3
(kPa)
1
mol
1
.
It is convenient to convert the value of
r
G

to the units cm
3
kPa mol
1
,
AQ: Kindly
provide closing
bracket

r
G

= 2.8678 kJ mol
1
_
8.315 10
2
dm
3
bar K
1
mol
1
8.315J K
1
mol
1

_
10
3
cm
3
dm
3
_

_
10
5
Pa
bar
_
.
(6)
r
G

= 2.8678 10
6
cm
3
kPa mol
1
.
Setting = p p

, eqns 2 and 36 give


2.8678 10
6
cm
3
kPa mol
1
(1.92 cm
3
mol
1
) +(7.80 10
8
cm
3
kPa
1
mol
1
)
2
= 0
TRAPP: CHAP04 2006/3/8 17:05 PAGE 93 #13
PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES 93
when
r
G( Tc , p) = 0. One real root of this equation is
= 1.60 10
6
kPa = p p

or
p = 1.60 10
6
kPa 10
2
kPa
= 1.60 10
6
kPa = 1.60 10
4
bar .
Above this pressure the reaction is spontaneous. The other real root is much higher: 2.3 10
7
kPa.
Question. What interpretation might you give to the other real root?