Combining multiple columns with same name in pandas dataframe

Try groupby with axis=1

df.groupby(df.columns.values, axis=1).agg(lambda x: x.values.tolist()).sum().apply(pd.Series).T.sort_values('pp')
Out[320]: 
          b   pp
0  0.001464  5.0
2  0.001459  5.0
1  0.001853  6.0
3  0.001843  6.0

A fun way with wide_to_long

s=pd.Series(df.columns)
df.columns=df.columns+s.groupby(s).cumcount().astype(str)

pd.wide_to_long(df.reset_index(),stubnames=['pp','b'],i='index',j='drop',suffix='\d+')
Out[342]: 
            pp         b
index drop              
0     0      5  0.001464
1     0      5  0.001459
0     1      6  0.001853
1     1      6  0.001843

This is possible using numpy:

res = pd.DataFrame({'pp': df['pp'].values.T.ravel(),
                    'b': df['b'].values.T.ravel()})

print(res)

          b  pp
0  0.001464   5
1  0.001459   5
2  0.001853   6
3  0.001843   6

---

Or without referencing specific columns explicitly:

res = pd.DataFrame({i: df[i].values.T.ravel() for i in set(df.columns)})

Let's use melt, cumcount and unstack:

dm = df.melt()
dm.set_index(['variable',dm.groupby('variable').cumcount()])\
  .sort_index()['value'].unstack(0)

Output:

variable         b   pp
0         0.001464  5.0
1         0.001459  5.0
2         0.001853  6.0
3         0.001843  6.0